PREPARATION AND ITS APPLICATION OF A CYANIDE-BRIDGED METAL ORGANIC COMPOUND WITH INTRAMOLECULAR MAGNETIC TRANSFORMATION
20230167144 · 2023-06-01
Inventors
Cpc classification
International classification
Abstract
This invention describes the preparation and its application of a cyanide bridged metal organic compound with intramolecular magnetic transition. The general structural formula of the compound is [(L2)(L1)M1(NC)M2(L3).sub.m(CN)M1(L1)(L2)](PF.sub.6).sub.6, n=2, 3, or 4. Damagnetic cyanidometal-bridge polynuclear compound [(L2)(L1)M1(NC)M(L)m(CN)M1(L1)(L2)](PF.sub.6).sub.2 is synthesized by compound M(L1)(L2)X (X=Cl, Br or I) with redox activity is selected as the terminal group fragment, and M(L).sub.2(CN).sub.2 is selected as the central bridging ligand, using solution. Carry out electrochemical research on compound [(L2)(L1)M1(NC)M(L)m(CN)M1(L1)(L2)](PF.sub.6).sub.2, select the appropriate oxidant, and obtain the one-electron oxidation product [(L2)(L1)M1(NC) M(L).sub.m(CN)M1(L1)(L2)](PF.sub.6).sub.3 and two-electron oxidation product [(L2)(L1)M1(NC)M(L).sub.m(CN)M1(L1)(L2)](PF.sub.6).sub.4. The cyanide-bridged metal organic compound is a cyanide bridged polynuclear compound that bridges by two diamagnetic metal fragments through a cyano group on a paramagnetic ion. According to its electrochemical and magnetic properties, it can be used for molecular-based magnetic materials. The preparation method is simple and the process conditions are easy to control.
Claims
1. A cyanide bridged metal organic compound with intramolecular magnetic transition, which is characterized in that its general structural formula is: [(L.sub.2)(L.sub.1)M.sub.1(NC)M.sub.2(L.sub.3).sub.m(CN)M.sub.1(L1)(L2)](PF.sub.6).sub.n; wherein L2 is cyclopentadiene anion or pentamethylcyclopentadiene anion; L1 is one selected from the group consisting of: bis(dimethylphosphine)methane, bis(diethylphosphine)methane, bis(dipropylphosphine)methane, bis(diisopropylphosphine)methane, bis(dibutylphosphine)methane, bis(diisopropyl)methane Butylphosphine) methane, bis(di-tert-butylphosphine)methane, bis(diphenylphosphine)methane, bis(dicyclopentylphosphino)methane, bis(dicyclohexylphosphine)methane, bis[(2-Methoxyphenyl) phenylphosphino] methane, 1,2-bis(dimethylphosphine)ethane, 1,2-bis(diethylphosphine)ethane, 1,2-bis(dipropylene) Phosphine) ethane, 1,2-bis(diisopropylphosphine)ethane, 1,2-bis(dibutylphosphine)ethane, 1,2-bis(diisobutylphosphine)ethane, 1,2-bis(di-tert-butylphosphine)ethane, 1,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(dicyclohexylphosphino)ethane, 1,2-Bis(diphenylphosphine)ethane, 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,3-bis(dimethylphosphine)propane, 1,3-Bis(diethylphosphine)propane, 1,3-bis(dipropylphosphine)propane, 1,3-bis(diisopropylphosphine)propane, 1,3-bis(dibutylphosphine)propane, 1,3-bis(diisobutylphosphine) propane, 1,3-bis(di-tert-butylphosphine)propane, 1,2-bis(dicyclopentylphosphino)propane, 1,3-bis(di Cyclohexylphosphino) propane, 1,3-bis(diphenylphosphine)propane, 1,3-bis[(2-methoxyphenyl)phenylphosphino]propane, 1,4-bis(dimethyl Phosphine) butane, 1,4-bis(diethylphosphine)butane, 1,4-bis(dipropylphosphine)butane, 1,4-bis(diisopropylphosphine)butane, 1,4-bis(dibutylphosphine)butane, 1,4-bis(diisobutylphosphine)butane, 1,4-bis(di-tert-butylphosphine)butane, 1,2-bis(di Cyclopentylphosphino)butane, 1,4-bis(dicyclohexylphosphine)butane, 1,4-bis(diphenylphosphine)butane and 1,4-bis[(2-methoxybenzene))phenylphosphino]butane; M.sub.1 and M.sub.2 are respectively one selected from the group consisting of manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium and iridium; m=1, 2 or 4, when m is a different value, L3 is a different ligand, the details are as follows: when m=4, L3 is one selected from the group consisting of: pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 1,5-lutidine, 1,4-lutidine, 1,3-lutidine, 1,2-lutidine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-nitropyridine, 3-nitropyridine, 4-nitropyridine, 2-tert-butylpyridine, 3-tert-butylpyridine, 4-tert-butylpyridine, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-one selected from the group consisting of bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-iodopyridine, 3-iodopyridine, 4-iodopyridine, 2-cyanopyridine, 3-cyanopyridine and 4-cyanopyridine; trimethyl phosphine, trimethoxy phosphine, dimethyl phosphine chloride, dimethyl phosphine bromide, triethyl phosphine, triethoxy phosphine, diethyl phosphine chloride, diethyl phosphine bromide, dimethyl phenyl phosphine, methyl phenyl phosphine chloride, methyl phenyl phosphine bromide, dimethoxy phenyl phosphine, methoxy phenyl phosphine chloride, methoxy phenyl phosphine bromide, two Ethyl phenyl phosphine, ethyl phenyl phosphine chloride, ethyl phenyl phosphine bromide, diethoxy phenyl phosphine, dipropyl phenyl phosphine, propyl phenyl phosphine chloride, propyl phenyl bromide phosphine, dipropoxyphenyl phosphine, diisopropyl phenyl phosphine, isopropyl phenyl phosphine chloride, isopropyl phenyl phosphine bromide, diisopropoxy phenyl phosphine, dibutoxy phenyl phosphine, dibutyl phenyl phosphine, butyl phenyl phosphine chloride, butyl phenyl phosphine bromide, diisobutoxy phenyl phosphine, diisobutyl phenyl phosphine, isobutyl phenyl chloride phosphine, isobutyl phenyl phosphine bromide, di-tert-butoxy phenyl phosphine, di-tert-butyl phenyl phosphine, tert-butyl phenyl phosphine chloride, tert-butyl phenyl phosphine bromide, dipentyl phenylphosphine, pentylphenylphosphonium chloride, pentylphenylphosphonium bromide, bis(2-cyanoethyl)phenylphosphine, 2-cyanoethylphenylphosphonium chloride, 2-cyanoethyl phenyl phosphine bromide, diphenyl methyl phosphine, diphenyl methoxy phosphine, diphenoxy methoxy phosphine, diphenoxy methyl phosphine, phenoxy methoxy phosphine chloride, benzene oxyl methoxy phosphine bromide, diphenoxy methyl phosphine bromide, diphenoxy methyl phosphine chloride, diphenyl ethyl phosphine, diphenyl ethoxy phosphine, diphenoxy ethoxy phosphine, diphenoxy ethyl phosphine, phenoxy ethoxy phosphine chloride, phenoxy ethoxy phosphine bromide, diphenoxy ethyl phosphine bromide, diphenoxy ethyl phosphine chloride, diphenyl propyl phosphine, diphenyl propoxy phosphine, diphenoxy propoxy phosphine, diphenoxy propyl phosphine, phenoxy propoxy phosphine chloride, phenoxy propoxy bromide phosphine, diphenoxypropyl phosphine bromide, diphenoxypropyl phosphine chloride, diphenyl isopropyl phosphine, diphenyl isopropoxy phosphine, diphenoxy isopropoxy phosphine, diphenoxyisopropylphosphine, phenoxyisopropyloxyphosphonium chloride, phenoxyisopropyloxyphosphonium bromide, diphenoxyisopropylphosphonium bromide, diphenoxyisopropyl chloride phosphine, diphenylbutylphosphine, diphenylbutoxyphosphine, diphenoxybutoxyphosphine, diphenoxybutylphosphine, phenoxybutoxyphosphine chloride, phenoxybutoxy phosphine bromide, diphenoxy butyl phosphine bromide, diphenoxy butyl phosphine chloride, diphenyl isobutyl phosphine, diphenyl isobutoxy phosphine, diphenoxy isobutoxy phosphine, diphenoxy isobutyl phosphine, phenoxy isobutoxy phosphine chloride, phenoxy isobutoxy phosphine bromide, diphenoxy isobutyl phosphine bromide, diphenoxy isobutyl phosphine chloride, diphenyl tert-butyl phosphine, diphenyl tert-butoxy phosphine, diphenoxy tert-butoxy phosphine, diphenoxy tert-butyl phosphine, phenoxy tert-butoxy chlorination phosphine, phenoxy iso-tert-oxy phosphine bromide, diphenoxy tert-butyl phosphine bromide, diphenoxy tert-butyl phosphine chloride, diphenyl pentyl phosphine, diphenyl pentyl oxy phosphine, diphenoxypentyloxyphosphine, diphenoxypentylphosphine, phenoxypentyloxyphosphine chloride, phenoxypentyloxyphosphine bromide, diphenoxypentylphosphine bromide, diphenoxy pentyl phosphine chloride, diphenyl isopentyl phosphine, diphenyl isopentyl phosphine, diphenoxy isopentyl phosphine, diphenoxy isopentyl phosphine, phenoxy isopentyl oxide phosphine chloride, phenoxy isopentyl phosphine bromide, diphenoxy isopentyl phosphine bromide, diphenoxy isopentyl phosphine chloride, diphenyl tert-amyl phosphine, diphenyl tert pentoxy phosphine, diphenoxy tert-pentyl phosphine, diphenoxy tert-pentyl phosphine, phenoxy tert-pentyloxy phosphine chloride, phenoxy iso-tert-oxy phosphine bromide, diphenoxy tert-amyl phosphine bromide, diphenoxy tert-amyl phosphine chloride, di-o-methyl phenyl methyl phosphine, di-o-methyl phenyl methoxy phosphine, di-o-methyl phenoxy methoxy phosphine, di-o-methylphenoxymethyl phosphine, o-methylphenoxy methoxy phosphine chloride, o-methyl phenoxy methoxy phosphonium bromide, di-o-methyl phenoxy methyl phosphonium bromide, di-o-methylphenoxymethyl phosphine chloride, di-o-methyl phenyl ethyl phosphine, di-o-methyl phenyl ethoxy phosphine, di-o-methyl phenoxy ethoxy phosphine, di-o-methyl phenoxyethyl phosphine, o-methylphenoxy ethoxy phosphine chloride, o-methylphenoxy ethoxy phosphonium bromide, di-o-methylphenoxy ethyl phosphonium bromide, di-o-methyl phenoxyethyl phosphine chloride, di-o-methyl phenyl propyl phosphine, di-o-methyl phenyl propoxy phosphine, di-o-methyl phenoxy propoxy phosphine, di-o-methyl phenoxy propyl phosphine, o-methylphenoxy propoxy phosphine chloride, o-methylphenoxy propoxy phosphonium bromide, di-o-methylphenoxy propyl phosphine bromide, di-o-methylphenoxy propyl phosphine chloride, di-o-methyl phenyl isopropyl phosphine, di-o-methyl phenyl isopropoxy phosphine, di-o-methyl phenoxy isopropoxy phosphine, di-o-methyl phenoxy iso propyl phosphine, o-tolu phenoxyisopropyl phosphine chloride, di-o-methyl phenyl butyl phosphine, di-o-methyl phenyl butoxy phosphine, di-o-methyl phenoxy butoxy phosphine, di-o-methyl phenoxy butyl phosphine, o-methylphenoxybutoxy phosphine chloride, o-methylphenoxybutoxy phosphonium bromide, di-o-methylphenoxybutyl phosphine bromide, di-o-methylphenoxy butyl phosphine chloride, di-o-methyl phenyl isobutyl phosphine, di-o-methyl phenyl isobutoxy phosphine, di-o-methyl phenoxy isobutoxy phosphine, di-o-methyl phenoxy iso butyl phosphine, o-methylphenoxy isobutoxy phosphine chloride, o-methylphenoxy isobutoxy phosphonium bromide, di-o-methylphenoxy isobutyl phosphine bromide, di-o-methyl phenoxy isobutyl phosphine chloride, di-o-methyl phenyl tert-butyl phosphine, di-o-methyl phenyl tert-butoxy phosphine, di-o-methyl phenoxy tert-butoxy phosphine, di-o-methyl phenoxy tert-butyl phosphine, o-methylphenoxy tert-butoxy phosphine chloride, o-methylphenoxy iso-tert-oxy phosphine bromide, di-o-methylphenoxy tert-butyl phosphine bromide, di-o-methylphenoxy tert-butyl phosphine chloride, di-o-methyl phenyl pentyl phosphine, di-o-methyl phenyl pentyl phosphine, di-o-methyl phenoxy pentyl oxy phosphine, di-o-methyl phenoxypentyl phosphine, o-methylphenoxypentyl phosphine chloride, o-methylphenoxypentyl phosphine bromide, di-o-methylphenoxypentyl phosphine bromide, di-o-methyl phenoxypentyl phosphine chloride, di-o-methyl phenyl isopentyl phosphine, di-o-methyl phenyl isopentyl phosphine, di-o-methyl phenoxy isopentyl phosphine, di-o-methyl phenoxy isopentyl phosphine, o-methylphenoxy isopentyl phosphine chloride, o-methylphenoxy isopentyl phosphine bromide, di-o-methylphenoxy isopentyl phosphine bromide, di-o-methylphenoxy isopentyl phosphine chloride, di-o-methyl phenyl tert-pentyl phosphine, di-o-methyl phenyl tert-pentyl phosphine, di-o-methyl phenoxy tert-pentyl phosphine, di-o-methylphenoxy tert-amyl phosphine, o-methylphenoxy tert-pentyloxy phosphine chloride, o-methylphenoxy tert-pentyloxy phosphonium bromide, di-o-methylphenoxy tert-amyl phosphine phosphine bromide, di-o-methylphenoxy tert-amyl phosphine chloride, dimethyl phenyl methyl phosphine, dimethyl phenyl methoxy phosphine, dimethyl phenoxy methoxy phosphine, dimethyl phenoxy methyl phosphine, m-methyl phenoxy methoxy phosphine chloride, m-methyl phenoxy methoxy phosphine bromide, dimethyl phenoxy methyl phosphine bromide, dimethylphenoxymethyl phosphine chloride, dimethyl phenyl ethyl phosphine, dimethyl phenyl ethoxy phosphine, dimethyl phenoxy ethoxy phosphine, dimethyl m-methylphenoxyethyl phosphine, m-methylphenoxy ethoxy phosphonium chloride, m-methylphenoxy ethoxy phosphonium bromide, dimethylphenoxyethyl phosphonium bromide, dimethyl phenoxyethyl phosphine bromide phenoxyethyl phosphine chloride, dimethyl phenyl propyl phosphine, dimethyl phenyl propoxy phosphine, dimethyl phenoxy propoxy phosphine, dimethyl phenoxy propyl phosphine, m-methylphenoxy propoxy phosphine chloride, m-methylphenoxy propoxy phosphonium bromide, dimethyl phenoxy propyl phosphine bromide, dimethyl phenoxy propyl phosphine chloride, dimethyl phenyl isopropyl phosphine, dimethyl phenyl isopropoxy phosphine, dimethyl phenoxy isopropoxy phosphine, dimethyl phenoxy iso propyl phosphine, m-methylphenoxy isopropoxy phosphine chloride, m-methylphenoxy isopropoxy phosphine bromide, dimethyl phenoxy isopropyl phosphine bromide, dimethyl phenoxy isopropyl phosphine bromide phenoxyisopropyl phosphine chloride, dimethyl phenyl butyl phosphine, dimethyl phenyl butoxy phosphine, dimethyl phenoxy butoxy phosphine, dimethyl phenoxy butyl phosphine, m-methylphenoxybutoxy phosphine chloride, m-methylphenoxybutoxy phosphonium bromide, dimethylphenoxybutyl phosphine bromide, dimethylphenoxy butyl phosphine chloride, dimethyl phenyl isobutyl phosphine, dimethyl phenyl isobutoxy phosphine, dimethyl phenoxy isobutoxy phosphine, dimethyl phenoxy iso butyl phosphine, m-methylphenoxy isobutoxy phosphine chloride, m-methylphenoxy isobutoxy phosphonium bromide, dimethyl phenoxy isobutyl phosphonium bromide, dimethyl phenoxy isobutyl phosphine bromide phenoxy isobutyl phosphine chloride, dimethyl phenyl tert-butyl phosphine, dimethyl phenyl tert-butoxy phosphine, dimethyl phenoxy tert-butoxy phosphine, dimethyl phenyl phenoxy tert-butyl phosphine, m-methylphenoxy tert-butoxy phosphine chloride, m-methylphenoxy iso-tert-oxy phosphine bromide, dimethylphenoxy tert-butyl phosphine bromide, dim-methylphenoxy tert-butyl phosphine chloride, dimethyl phenylpentyl phosphine, dimethyl phenyl pentyl phosphine, dimethyl phenoxy pentyl phosphine, dimethyl phenoxypentyl phosphine, m-methylphenoxypentyl phosphine chloride, m-methylphenoxypentyl phosphine bromide, dimethylphenoxypentyl phosphine bromide, dimethyl phenoxypentyl phosphine bromide phenoxypentyl phosphine chloride, dimethyl phenyl isopentyl phosphine, dimethyl phenyl isopentyl phosphine, dimethyl phenoxy isopentyl phosphine, dimethyl phenoxy isopentyl phosphine, m-methylphenoxy isopentyl phosphine chloride, m-methylphenoxy isopentyl phosphine bromide, dimethyl phenoxy isopentyl phosphine bromide, dim-methylphenoxy isopentyl phosphine chloride, dimethyl phenyl tert-pentyl phosphine, dimethyl phenyl tert-pentyl phosphine, dimethyl phenoxy tert-pentyl phosphine, dim-methylphenoxy tert-amyl phosphine, m-methylphenoxy tert-amyloxy phosphine chloride, m-methylphenoxy tert-amyloxy phosphonium bromide, dimethylphenoxy tert-amyl phosphine phosphine bromide, di-m-methylphenoxy tert-amyl phosphine chloride, di-p-tolyl methyl phosphine, di-p-tolyl methoxy phosphine, di-p-tolyl oxy methoxy phosphine, two-p-tolyl tolyloxymethyl phosphine, p-tolyloxy methoxy phosphine chloride, p-tolyloxy methoxy phosphine bromide, di-p-tolyloxy methyl phosphine bromide, di-p-tolyloxy methyl phosphine chloride, di-p-tolyl ethyl phosphine, di-p-tolyl ethoxy phosphine, di-p-tolyloxy ethoxy phosphine, di-p-tolyl oxy ethyl phosphine, p-tolyl oxygen ethoxy phosphine chloride, p-tolyloxy ethoxy phosphonium bromide, di-p-tolyloxy ethyl phosphonium bromide, di-p-tolyloxy ethyl phosphine chloride, di-p-tolyl propyl phosphine, di-p-tolyl propoxy phosphine, di-p-tolyloxy propoxy phosphine, di-p-tolyloxy propyl phosphine, p-tolyloxy propoxy phosphine chloride, p-tolyloxy propoxy phosphine bromide, di-p-tolyloxy propyl phosphine bromide, di-p-tolyloxy propyl phosphine chloride, di-p-tolyl isopropyl phosphine, di-p-tolyl isopropoxy phosphine, di-p-tolyloxy isopropoxy phosphine, di-p-tolyloxy isopropyl phosphine, p-tolyloxy isopropoxy phosphine chloride, p-tolyloxy isopropoxy bromide phosphine, di-p-tolyloxy isopropyl phosphine bromide, di-p-tolyloxy isopropyl phosphine chloride, di-p-tolyl butyl phosphine, di-p-tolyl butoxy phosphine, di-p-toluene oxybutoxy phosphine, di-p-tolyloxy butyl phosphine, p-tolyloxy butoxy phosphine chloride, p-tolyloxy butoxy phosphine bromide, di-p-tolyloxy butyl phosphine bromide, two-p-tolyloxybutyl phosphine chloride, two-p-tolyl isobutyl phosphine, two-p-tolyl isobutoxy phosphine, two p-tolyloxy isobutyl phosphine, p-tolyloxy isobutoxy phosphine chloride, p-tolyloxy isobutoxy phosphonium bromide, two p-tolyloxy isobutyl phosphine bromide, two p-tolyloxy isobutyl phosphine chloride, di-p-tolyl tert-butyl phosphine, di-p-tolyl tert-butoxy phosphine, di-p-tolyloxy tert-butoxy phosphine, di-p-tolyl oxygen tert-butyl phosphine, p-tolyloxy tert-butoxy phosphine chloride, p-tolyloxy iso-tert-oxy phosphonium bromide, di-p-tolyloxy tert-butyl phosphine bromide, di-p-tolyloxy tert-butyl phosphine chloride, di-p-tolyl pentyl phosphine, di-p-tolyl pentyl phosphine, di-p-tolyl oxypentyl phosphine, di-p-tolyl pentyl phosphine, p-toluene oxypentyloxy phosphine chloride, p-tolyloxy pentyl phosphine bromide, di-p-tolyloxy pentyl phosphonium bromide, di-p-tolyloxy pentyl phosphine chloride, di-p-tolyl 2-methyl isopentyl phosphine, di-p-tolyl isopentoxy phosphine, di-p-tolyloxy isopentyl phosphine, di-p-tolyloxy isopentyl phosphine, p-tolyloxy isopentoxy chloride phosphine bromide, p-tolyloxy isopentyl phosphine bromide, di-p-tolyloxy isopentyl phosphine bromide, di-p-tolyloxy isopentyl phosphine chloride, di-p-tolyl tert-pentyl phosphine, di-p-tolyl tert-pentyl phosphine, di-p-tolyl oxy tert-pentyl phosphine, di-p-tolyl tert-pentyl phosphine, p-tolyloxy tert-pentyl phosphine chloride, p-tolyloxy tert-pentyl phosphine bromide, two-p-tolyloxy tert-pentyl phosphine bromide, two-p-tolyl oxy tert-amyl phosphine chloride, diphenyl (trimethylsilyl) phosphine, phenyl (trimethylsilyl) phosphine chloride, phenyl (trimethylsilyl) phosphine bromide, allyl diphenyl phosphine, allyl phenyl phosphine chloride, allyl phenyl phosphine bromide, diphenyl cyclohexyl phosphine, diphenoxy cyclohexyl phosphine, phenoxy cyclohexyl phosphine chloride, phenoxy cyclohexyl phosphine bromide, phenylcyclohexyl phosphine bromide, phenylcyclohexyl phosphine chloride, bis(3,5-dimethylphenyl)methylphosphine, (3,5-dimethylphenyl)methyl phosphine chloride, (3,5-dimethylphenyl)methylphosphonium bromide, bis(3,5-dimethylphenyl)methoxyphosphine, bis(3,5-dimethylphenyl)) methoxy phosphine bromide, bis(3,5-dimethylphenyl) methoxyphosphine chloride, bis(3,5-dimethylphenyl)ethyl phosphine, (3,5-dimethylphenyl) phenyl) ethyl phosphine chloride, (3,5-dimethylphenyl) ethyl phosphine bromide chloride, bis(3,5-dimethylphenyl) ethoxyphosphine, (3,5-dimethylphenyl)ethoxyphosphonium bromide, (3,5-dimethylphenyl)ethoxyphosphonium chloride, bis(3,5-dimethylphenyl)propylphosphine, (3,5-dimethylphenyl)propylphosphonium chloride, (3,5-dimethylphenyl)propylphosphonium bromide chloride, bis(3,5-dimethylphenyl)propoxyphosphine, (3,5-dimethylphenyl)propoxyphosphonium bromide, (3,5-dimethylphenyl)propoxyphosphonium chloride, bis(3,5-dimethylphenyl)iso propylphosphine, (3,5-dimethylphenyl) isopropyl phosphine chloride, (3,5-dimethylphenyl) isopropyl phosphine bromide chloride, bis(3,5-dimethylphenyl) phenyl)isopropoxyphosphine, (3,5-dimethylphenyl)isopropoxyphosphine bromide, (3,5-dimethylphenyl)isopropoxyphosphine chloride, bis(3,5-dimethylphenyl)butylphosphine, (3,5-dimethylphenyl)butylphosphine chloride, (3,5-dimethylphenyl); when m=2, L3 is one selected from the group consisting of: 2,2′-dipyridine, 3-methyl-2,2′-dipyridine, 4-methyl-2,2′-dipyridine, 5-methyl-2,2′-Bipyridine, 6-methyl-2,2′-bipyridine, 4-chloro-2,2′-bipyridine, 5-chloro-2,2′-bipyridine, 6-chloro-2,2′-bipyridine, 4-bromo-2,2′-bipyridine, 5-bromo-2,2′-bipyridine, 6-bromo-2,2′-bipyridine, 4-methoxy-2,2′-bipyridine, 5-methoxy-2,2′-bipyridine, 6-methoxy-2,2′-bipyridine, 4-cyano-2,2′-bipyridine, 5-cyano-2,2′-bipyridine, 6-cyano-2,2′-bipyridine, 4-tert-butyl-2,2′-bipyridine, 5-tert-butyl-2,2′-bipyridine, 6-tert-butyl-2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, 5,5′-dimethyl-2,2′-bipyridine, 6,6′-dimethyl-2,2′-bipyridine, 4,4′-dicyano-2,2′-bipyridine, 5,5′-dicyano-2,2′-bipyridine, 6,6′-dicyano-2,2′-bipyridine, 4,4′-dimethoxy-2,2′-bipyridine, 5,5′-dimethoxy-2,2′-bipyridine, 6,6′-dimethoxy-2,2′-bipyridine, 4,4′-di-tert-butyl-2,2′-bipyridine, 5,5′-dipyridine tert-butyl-2,2′-bipyridine, 6,6′-di-tert-butyl-2,2′-bipyridine, 4,4′-dichloro-2,2′-bipyridine, 5,5′-dichloro-2,2′-bipyridine, 6,6′-dichloro-2,2′-bipyridine, 4,4′-dibromo-2,2′-bipyridine, 5,5′-dipyridine bromo-2,2′-bipyridine, 6,6′-dibromo-2,2′-bipyridine, 2,2′-biquinoline, 4,4′-diphenyl-2,2′-bipyridine pyridine, 1,10-phenanthroline, 2-chloro-1,10-phenanthroline, 3-chloro-1,10-phenanthroline, 4-chloro-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 2-bromo-1,10-phenanthroline, 3-bromo-1,10-phenanthroline, 4-bromo-1,10-phenanthroline phenanthroline, 5-bromo-1,10-phenanthroline, 2-methyl-1,10-phenanthroline, 3-methyl-1,10-phenanthroline, 4-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2-methoxy-1,10-phenanthroline, 3-methoxy-1,10-phenanthroline, 4-methoxy-1,10-phenanthroline, 5-methoxy-1,10-phenanthroline, 2-cyano-1,10-phenanthroline, 3-cyano-1,10-phenanthroline, 4-cyano-1,10-phenanthroline, 5-cyano-1,10-phenanthroline, 2-nitro-1,10-phenanthroline, 3-nitro-1,10-phenanthroline, 4-nitro-1,10-phenanthroline, 5-nitro base-1,10-phenanthroline, 2-tert-butyl-1,10-phenanthroline, 3-tert-butyl-1,10-phenanthroline, 4-tert-butyl-1,10-phenanthroline, 5-tert-butyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-dichloro-1,10-phenanthroline, 3,8-dichloro-1,10-phenanthroline, 4,7-dichloro-1,10-phenanthroline, 5,6-dichloro-1,10-phenanthroline, 3,4,7,8-tetrachloro-1,10-phenanthroline, 2,9-dibromo-1,10-phenanthroline, 3,8-dibromo-1,10-phenanthroline, 4,7-dibromo-1,10-phenanthroline, 5,6-dibromo-1,10-phenanthroline, 3,4,7,8-tetrabromo-1,10-phenanthroline, 2,9-dimethoxy-1,10-phenanthroline, 3,8-dimethoxy-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, 5,6-dimethoxy-1,10-phenanthroline, 3,4,7,8-tetramethoxy-1,10-phenanthroline, 2,9-dicyano-1,10-phenanthroline, 3,8-dicyano-1,10-phenanthroline, 4,7-dicyano-1,10-phenanthroline, 5,6-dicyano-1,10-phenanthroline, 3,4,7,8-tetracyano 1,10-phenanthroline, 2,9-dinitro-1,10-phenanthroline, 3,8-dinitro-1,10-phenanthroline, 4,7-dinitro-1,10-phenanthroline, 5,6-dinitro-1,10-phenanthroline, 3,4,7,8-tetranitro-1,10-phenanthroline, bis(dimethylphosphine)methane, bis(diethylphosphine)methane, bis(dipropylphosphine)methane, bis(diisopropylphosphine)methane, bis(dibutylphosphine)methane, bis(diisopropyl)methane butylphosphine) methane, bis(di-tert-butylphosphine)methane, bis(diphenylphosphine)methane, bis(dicyclopentylphosphino)methane, bis(dicyclohexylphosphino)methane, bis(diphenyl) phosphine) methane, bis[(2-methoxyphenyl)phenylphosphino]methane, 1,2-bis(dimethylphosphine)ethane, 1,2-bis(diethylphosphine)ethane, 1,2-bis(dipropylphosphine)ethane, 1,2-bis(diisopropylphosphine)ethane, 1,2-bis(dibutylphosphine)ethane, 1,2-bis(Diisobutylphosphine) ethane, 1,2-bis(di-tert-butylphosphine)ethane, 1,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(dicyclohexyl) phosphine) ethane, 1,2-bis(diphenylphosphine)ethane, 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,3-bis(diphenylphosphine)ethane methylphosphine) propane, 1,3-bis(diethylphosphine) propane, 1,3-bis(dipropylphosphine) propane, 1,3-bis(diisopropylphosphine) propane, 1,3-bis(dibutylphosphine)propane, 1,3-bis(diisobutylphosphine)propane, 1,3-bis(di-tert-butylphosphine)propane, 1,2-bis(dicyclopentylphosphino)propane, 1,3-bis(dicyclohexylphosphino)propane, 1,3-bis(diphenylphosphine)propane, 1,3-bis[(2-methoxyphenyl)phenylphosphino]propane, 1,4-bis(dimethylphosphine)butane, 1,4-bis(diethylphosphine)butane, 1,4-bis(di propylphosphine) butane, 1,4-bis(diisopropylphosphine)butane, 1,4-bis(dibutylphosphine)butane, 1,4-bis(diisobutylphosphine)butane, 1,4-bis(di-tert-butylphosphino)butane, 1,2-bis(dicyclopentylphosphino)butane, 1,4-bis(dicyclohexylphosphino)butane, 1,4-one of bis(diphenylphosphine)butane and 1,4-bis[(2-methoxyphenyl)phenylphosphino]butane; when m=1, L3 is one selected from the group consisting of: 2,2′:6′,2″:6″,2′″-tetrabipyridine, 2-methyl-2,2′:6′,2″:6″,2″-tetrapyridine, 3-methyl-2,2′:6′,2″:6″,2′-tetrapyridine, 4-methyl-2,2′:6′,2″:6″,2′″-tetrabipyridine, 5-methyl-2,2′:6′,2″:6″,2′″-tetra bipyridine, 6-methyl-2,2′:6′,2″:6″,2′″-tetrabipyridine, 7-methyl-2,2′:6′,2″:6″,2′″-tetrapyridine, 8-methyl-2,2′:6′,2″:6″,2′″-tetrapyridine, 2-methoxy-2,2′:6′,2″:6″,2′″-tetrabipyridine, 3-methoxy-2,2′:6′,2″:6″,2′″-tetrapyridine, 4-methoxy-2,2′:6′,2″:6″,2′″-tetrapyridine, 5-methoxy-2,2′:6′,2″:6″,2′″-tetrapyridine, 6-methoxy-2,2′:6′,2″:6″,2′″-Tetrapyridine, 7-methoxy-2,2′:6′,2″:6″,2′″-tetrabipyridine, 8-methoxy-2,2′:6′,2″:6″,2′″-tetrapyridine, 2-nitro-2,2′:6′,2″:6″,2′″-tetrapyridine, 3-nitro-2,2′:6′,2″:6″,2″-tetrabipyridine, 4-nitro-2,2′:6′,2″:6″,2′″-tetrabipyridine, 5-nitro-2,2′:6′,2″:6″,2″-tetrabipyridine, 6-nitro-2,2′:6′,2″:6″,2′″-tetrapyridine, 7-nitro-2,2′:6′,2″:6″,2″-tetrapyridine, 8-nitro-2,2′: 6′,2″:6″,2″-tetrabipyridine, 2-cyano-2,2′:6′,2″:6″,2′″-tetrabipyridine, 3-cyano-2,2′:6′,2″:6″,2′″-tetrabipyridine, 4-cyano-2,2′:6′,2″:6″,2′″-tetrapyridine, 5-cyano-2,2′:6′,2″:6″,2′″-tetrapyridine, 6-cyano-2,2′:6′,2″:6″,2′″-tetrabipyridine, 7-cyano-2,2′:6′,2″:6″,2′″-tetrabipyridine, 8-cyano-2,2′:6′,2″:6″,2′″-tetrabipyridine, 2-chloro-2,2′:6′,2″:6″,2′″-tetrabipyridine, 3-chloro-2,2′:6′,2″:6″,2′″-tetrabipyridine, 4-chloro-2,2′:6′,2″:6″,2′″-tetrapyridine, 5-chloro-2,2′:6′,2″:6″,2′″-tetrabipyridine, 6-chloro-2,2′:6′,2″:6″,2′″-tetrapyridine, 7-chloro-2,2′:6′,2″:6″,2′″-tetrapyridine, 8-chloro-2,2′:6′,2″:6″,2′″-tetrapyridine, 2-bromo-2,2′:6′,2″:6″,2′″-tetrapyridine, 3-bromo-2,2′:6′,2″:6″,2′″-tetrabipyridine, 4-bromo-2,2′:6′,2″:6″,2′″-tetra bipyridine, 5-bromo-2,2′:6′,2″:6″,2′″-tetrabipyridine, 6-bromo-2,2′:6′,2″:6″,2′″-tetrabipyridine, 7-bromo-2,2′:6′,2″:6″,2′″-tetrabipyridine and 8-bromo-2,2′:6′,2″:6″,2″-tetrapyridine; n=2, 3, or 4.
2. A method for preparing a cyanide-bridged metal organic compound with intramolecular magnetic transition according to claim 1, comprising the following steps: (1) under argon atmosphere, adding M.sub.1(L.sub.3).sub.m(CN).sub.2 to alcohol, nitrile or ketone solvent, then M.sub.2(L.sub.1)(L.sub.2)X is added, where X is Cl, Br or I; after reacting the resulting mixture at 50-120° C. for 5-24 hours, NH.sub.4PF.sub.6 is then added to prepare a diamagnetic cyanide bridged metal organic compound [(L.sub.2)(L.sub.1)M.sub.1(NC-μ)M.sub.2(L.sub.3).sub.m(μ-CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.2; (2) dissolving [(L.sub.2)(L.sub.1)M.sub.1(NC)M.sub.2(L.sub.3).sub.m(CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.2 in the halogenated hydrocarbon solvent, then oxidant A is added, reacting at 20-80° C. for 1-12 hours, the paramagnetic cyanide bridged metal organic compound [(L.sub.2)(L.sub.1)M.sub.1(NC)M.sub.2(L.sub.3).sub.m(CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.3 is obtained; (3) dissolving [(L.sub.2)(L.sub.1)M.sub.1(NC)M.sub.2(L.sub.3).sub.m(CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.3 in a halogenated hydrocarbon solvent, oxidant B is added, reacting at 20-80° C. for 1-12 hours to prepare antiferromagnetic or ferromagnetic cyanide bridged metal organic compound [(L.sub.2)(L.sub.1)M.sub.1 (NC)M.sub.2(L.sub.3).sub.m(CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.4.
3. The preparation method of cyano-bridged metal organic compound with intramolecular magnetic transition according to claim 2, it is characterized in that: the alcohol solvent is one selected from the group consisting of: methanol, ethanol, propanol, isopropanol, butanol, tertiary one selected from the group consisting of butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol and 3-hexanol; nitrile solvent is one selected from the group consisting of: acetonitrile, propionitrile, butyronitrile and valeronitrile; ketone solvent is one selected from the group consisting of: acetone, methyl ethyl ketone, n-pentanone and hexanone.
4. The preparation method of cyanide bridged metal organic compound with intramolecular magnetic transition according to claim 2, characterized in that: the halogenated hydrocarbon is monochloromethane, dichloromethane, trichloromethane, tetrachloride one selected from the group consisting of carbon, ethyl chloride, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, and 1,2-dichloropropane.
5. The preparation method of cyanide bridged metal organic compound with intramolecular magnetic transition according to claim 2, characterized in that: the oxidant A and the oxidant B is one selected from the group consisting of oxyacetic acid, sodium dichromate, chromic acid, peroxy ammonium sulfate, sodium hypochlorite, sodium percarbonate, sodium perborate, potassium perborate, Na.sub.2O.sub.2, K.sub.2O.sub.2, MgO.sub.2, CaO.sub.2, BaO.sub.2, H.sub.2O.sub.2, F.sub.2, Cl.sub.2, O.sub.2, O.sub.3, Br.sub.2, 1.sub.2, 5, Si, KMnO.sub.4, KClO.sub.3, H.sub.2SO.sub.4, HNO.sub.3, MnO.sub.2, FeCl.sub.3, Fe(NO.sub.3).sub.3, Fe(ClO.sub.4).sub.3, Fe(BF.sub.4).sub.3, Fe(PF.sub.6).sub.3, CpFe(BF.sub.4), CpFe(PF.sub.6), RuCb, Ru(NO.sub.3).sub.3, Ru(ClO.sub.4).sub.3, Ru(BF.sub.4).sub.3, Ru(PF.sub.6).sub.3, CpRu(BF.sub.4), CpRu(PF.sub.6), Cu(ClO.sub.4).sub.2, CuCl.sub.2, Cu(PF.sub.6).sub.2, Cu(BF.sub.4).sub.2, Cu(NO.sub.3).sub.2, CpCu(BF.sub.4), CpCu(PF.sub.6), AgNO.sub.3, AgPF.sub.6 and AgBF.sub.4.
6. The preparation method of cyanide bridged metal organic compound with intramolecular magnetic transition according to claim 2, characterized in that: the molar ratio of M.sub.1(L.sub.3).sub.m(CN).sub.2, M.sub.2(L.sub.1)(L.sub.2)X and NH.sub.4PF.sub.6 is 1:1.01-4.99:1.02-4.99, the ratio of [(L.sub.2)(L.sub.1)M.sub.1(NC)M.sub.2(L.sub.3).sub.4CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.2 and oxidant A is 1:0.49-1.99, the molar ratio of [(L.sub.2)(L.sub.1)M.sub.1(NC)M.sub.2(L.sub.3).sub.4CN)M.sub.1(L.sub.1)(L.sub.2)](PF.sub.6).sub.3 to oxidant B is 1:0.99-3.99.
7. The use of the cyano-bridged metal organic compound with intramolecular magnetic transition of claim 1 as a magnetic material.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038] 1 represents trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2, 2 represents trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3, 3 represents trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4.
[0039]
[0040]
[0041]
DETAILED DESCRIPTION OF EMBODIMENTS
[0042] The invention will be described in detail below in conjunction with specific embodiments. The following embodiments are only used to illustrate the present invention and not to limit the scope of the present invention.
Example 1
trans-[Cp(dppe)Fe.SUP.II.(NC)Ru.SUP.II.(.SUP.tbu.py).SUP.4.(CN)Fe.SUP.II.(dppe)Cp][PF.SUB.6.].SUB.2..3CH.SUB.2.Cl.SUB.2
[0043] Under argon atmosphere, a mixture of trans-Ru.sup.II(.sup.tbupy).sub.4(CN).sub.2 (100 mg, 0.144 mmol) and CpFe.sup.II(dppe)(NCCH.sub.3)Br (186 mg, 0.290 mmol) was added to CH.sub.3OH (10 ml) at room temperature, resulting in a red solution. And the mixture stirred at 60° C. for 6 h, NH.sub.4PF.sub.6 (51.7 mg, 0.317 mmol) was then added to the above red reaction solution. A red precipitate appeared immediately and was collected. Red prism crystals 1 (121 mg, 37%) suitable for X-ray diffraction analysis were obtained from a mixed solution of dichloromethane and ethyl ether (1:3, 40 ml) at room temperature. Anal. Calcd for C.sub.100H.sub.110F.sub.12Fe.sub.2N.sub.6PF.sub.6Ru: C, 59.38; H, 5.48; N, 4.16%. Found: C, 58.84; H, 5.71; N, 4.12%. IR (ν.sub.CN, KBr pellet, cm.sup.−1): 2071. UV-vis (CH.sub.3CN), λ.sub.max, nm (ε, dm.sup.3 mol.sup.−1 cm.sup.−1): 476 (1214). MS, m/z: 519.5 [Fe.sup.II(dppe)Cp]+, 1212.3 [1-Fe.sup.II(dppe)Cp-2PF.sub.6].sup.+, 1876.4 [1-PF.sub.6].sup.+.
trans-[Cp(dppe)Fe.SUP.III.(NC)Ru.SUP.II.(.SUP.tbu.py).SUP.4.(CN)Fe.SUP.II.(dppe)Cp][PF.SUB.6.].SUB.3..2C.SUB.3.H.SUB.8.O.H.SUB.2.O
[0044] Cp.sub.2Fe.sup.III(PF.sub.6) (14.6 mg, 0.044 mmol) was added to a solution of 1 (100 mg, 0.044 mol) in dichloromethane (10 ml) at room temperature. The mixture was stirred at 30° C. for 3 h and concentrated to 2 ml under reduced pressure, and then diethyl ether (20 ml) was added and a red precipitate was obtained. The resultant residue was dissolved in a mixed solution of dichloromethane (10 ml), diethyl-ether (30 ml) and 2-propanol (1 ml), to give 2 as red crystals (27.2 mg, 27%). Anal. Calcd for C.sub.106H.sub.128F.sub.18Fe.sub.2N.sub.6O.sub.3P.sub.7Ru: C, 55.22; H, 5.60; N, 3.64%. Found: C, 55.33; H, 5.42; N, 3.53%. IR (ν.sub.CN, KBr pellet, cm.sup.−1): 2068, 2011. UV-vis (CH.sub.3CN), λ.sub.max, nm (ε, dm.sup.3 mol.sup.−1 cm.sup.−1): 465 (1468), 957 (2381). MS, m/z: 519.8 [CpFe.sup.II(dppe)].sup.+, 1212.1 [2-CpFe.sup.III(dppe)-3PF.sub.6]+, 1359.6 [2-CpFe.sup.II(dppe)-2PF.sub.6].sup.+, 2021.1 [2-PF.sub.6].sup.+.
trans-[Cp(dppe)Fe.SUP.III.(NC)Ru.SUP.II.(.SUP.tbu.py).SUB.4.(CN)Fe.SUP.III.(dppe)Cp][PF.SUB.6.].SUB.4..3 C.SUB.3.H.SUB.6.O.3CH.SUB.3.CN
[0045] To a solution of 2 (100.0 mg, 0.044 mmol) in dichloromethane (10 ml), AgPF.sub.6 (12.2 mg, 0.048 mmol) was added at room temperature. The solution changed immediately from red to brown and was stirred for another 3 h at 30° C. and concentrated under a reduced pressure to obtain a black brown precipitate. The black brown precipitate was collected, and washed with a little dichloromethane and ethyl ether. Deep brown prism crystals of 3 (37.4 mg, 32%) suitable for single crystal X-ray diffraction analysis were grown by layering diethyl ether (30 ml) on the acetone (10 ml) solution of the precipitate at room temperature in the dark. Anal. Calcd for C.sub.115H.sub.143F.sub.24Fe.sub.2N.sub.9O.sub.3P.sub.8Ru: C, 52.80; H, 5.51%; N, 4.82%. Found: C, 52.94; H, 5.43; N, 4.54%. IR (ν.sub.c\.sub.r, KBr pellet, cm.sup.−1): 2018. UV-vis (CH.sub.3CN), λ.sub.max,nm (ε, dm.sup.3 mol.sup.−1 cm.sup.−1): 468(1980), 780(5573). MS, m/z: 1357.2 [3-CpFe.sup.III(dppe)-3PF.sub.6].sup.+, 2166.0 [3-PF.sub.6].sup.+.
[0046] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2, 3, 4) prepared in this example was mixed in acetone and ether, etc. After recrystallization in a solvent, a crystal suitable for X-ray single crystal diffraction is obtained, which is subjected to single crystal X-ray diffraction analysis. The crystal structure diagram of the cation is shown in
[0047] The main crystallographic data of trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6] (n=2, 3, 4) prepared in this example are shown in Table 1 As shown, and the main bond length and bond angle are shown in Table 2.
TABLE-US-00001 TABLE 1 Crystallographic Data and Details of Structure Determination for Complexes 1-3 Complex trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 CCDC NO. 1989022 Chemical formula C.sub.103H.sub.116Cl.sub.6F.sub.12Fe.sub.2N.sub.6P.sub.6Ru Formula weight 2277.30 Colour and Habit Red prism Crystal Size/mm 0.48 × 0.37 × 0.11 T/K 123 Crystal system Monoclinic Space group P2.sub.1/c a/Å 13.838(3) b/Å 30.951(8) c/Å 25.870(7) α/deg 90.00 β/deg 96.100(6) γ/deg 90.00 V/Å.sup.3 11017(5) Z 4 ρ.sub.calcd(g/cm.sup.3) 1.373 λ (Mo K.sub.α, Å) 0.71073 μ(Mo K.sub.α, mm.sup.−1) 0.695 Completeness 99.5% F(000) 4688 h, k, l, range −16 ≤ h ≤ 15, −36 ≤ k ≤ 36, −30 ≤ l ≤ 28 θ range/deg 2.15-25.00 Reflections measured 19323 R.sub.int 0.0706 Params/restraints/Data(obs.) 1306/195/15343 GOF 1.067 R.sub.1, .sub.ωR.sub.2 (I > 2 σ (I)) 0.0801, 0.1966 R.sub.1, .sub.ωR.sub.2 (all data) 0.1018, 0.2146 Complex trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3 CCDC NO. 1989024 Chemical formula C.sub.106H.sub.128F.sub.18Fe.sub.2N.sub.6O.sub.3P.sub.7Ru Formula weight 2305.68 Colour and Habit Red prism Crystal Size/mm 0.51 × 0.38 × 0.18 T/K 123 Crystal system Monoclinic Space group P2.sub.1/n a/Å 13.0216(17) b/Å 32.214(5) c/Å 27.028(4) α/deg 90.00 β/deg 98.184(3) γ/deg 90.00 V/Å.sup.3 11222(3) Z 4 ρ.sub.calcd(g/cm.sup.3) 1.361 λ (Mo K.sub.α, Å) 0.71073 μ(Mo K.sub.α, mm.sup.−1) 0.568 Completeness 99.6% F(000) 4748 h, k, l, range −15 ≤ h ≤ 14, −38 ≤ k ≤ 37, −32 ≤ l ≤ 32 θ range/deg 2.08-25.00 Reflections measured 19688 R.sub.int 0.0409 Params/restraints/Data(obs.) 1423/767/16964 GOF 1.053 R.sub.1, .sub.ωR.sub.2 (I > 2 σ (I)) 0.0736, 0.2024 R.sub.1, .sub.ωR.sub.2 (all data) 0.0838, 0.2137 Complex trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 CCDC NO. 1989023 Chemical formula C.sub.115H.sub.143F.sub.24Fe.sub.2N.sub.9O.sub.3P.sub.8Ru Formula weight 2615.91 Colour and Habit Brown prism Crystal Size/mm 0.49 × 0.33 × 0.23 T/K 123 Crystal system Orthorhombic Space group Pbca a/Å 28.530(6) b/Å 26.984(5) c/Å 34.406(7) α/deg 90.00 β/deg 90.00 γ/deg 90.00 V/Å.sup.3 26487(9) Z 8 ρ.sub.calcd(g/cm.sup.3) 1.312 λ (Mo K.sub.α, Å) 0.71073 μ(Mo K.sub.α, mm.sup.−1) 0.508 Completeness 99.5% F(000) 10816 h, k, l, range −33 ≤ h ≤ 33, −29 ≤ k ≤ 32, −40 ≤ l ≤ 40 θ range/deg 2.05-25.00 Reflections measured 23181 R.sub.int 0.0892 Params/restraints/Data(obs.) 1558/482/18248 GOF 1.068 R.sub.1, .sub.ωR.sub.2 (I > 2 σ (I)) 0.0917, 0.2182 R.sub.1, .sub.ωR.sub.2 (all data) 0.1119, 0.2351 Complex trans-Ru(.sup.tbupy).sub.4(CN).sub.2 CCDC NO. 1989021 Chemical formula C.sub.38H.sub.62N.sub.6O.sub.5Ru Formula weight 783.92 Colour and Habit Orange prism Crystal Size/mm 0.31 × 0.15 × 0.14 T/K 123 Crystal system Trigonal Space group R-3 a/Å 25.887(8) b/Å 25.887(8) c/Å 15.915(6) α/deg 90.00 β/deg 90.00 γ/deg 120.00 V/Å.sup.3 9236(6) Z 9 ρ.sub.calcd(g/cm.sup.3) 1.252 λ (Mo K.sub.α, Å) 0.71073 μ(Mo K.sub.α, mm.sup.−1) 0.428 Completeness 97.9% F(000) 3654 h, k, l, range −33 ≤ h ≤ 33, −33 ≤ k ≤ 33, −20 ≤ l ≤ 20 θ range/deg 2.72-27.45 Reflections measured 4608 R.sub.int 0.0663 Params/restraints/Data(obs.) 354/84/4434 GOF 1.025 R.sub.1, .sub.ωR.sub.2 (I > 2 σ (I)) 0.0534, 0.1472 R.sub.1, .sub.ωR.sub.2 (all data) 0.0550, 0.1512
R.sub.1=Σ∥F.sub.o|−|F.sub.c∥/Σ|F.sub.o|. .sub.ωR.sub.2=[Σ[.sub.ω(F.sub.o.sup.2−F.sub.c.sup.2).sup.2]/Σ[.sub.ω(F.sub.o.sup.2).sup.2]].sup.1/2.
TABLE-US-00002 TABLE 2 Selected Bond Lengths ({acute over (Å)}) and Bond Angles (deg) for Complexes 1-3 trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 Ru1—C1 2.037(6) Ru1—C2 2.046(6) Ru1—N3 2.108(5) Ru1—N4 2.093(4) Ru1—N5 2.101(5) Ru1—N6 2.105(5) C1≡N1 1.164(7) C2≡N2 1.161(7) Fe1—N1 1.934(5) Fe2—N2 1.924(5) Fe1—P1 2.199(2) Fe1—P2 2.205(2) Fe2—P3 2.197(2) Fe2—P4 2.203(2) C1—Ru1—C2 178.7(2) N1≡C1—Ru1 176.4(5) N2≡C2—Ru1 176.9(5) C1≡N1—Fe1 173.5(5) C2≡N2—Fe2 173.3(4) Fe1 . . . Ru1 5.121 Fe2 . . . Ru1 5.116 Fe1 . . . Fe2 10.228 trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3 Ru1—C1 2.051(5) Ru1—C2 1.989(4) Ru1—N3 2.108(4) Ru1—N4 2.092(4) Ru1—N5 2.101(4) Ru1—N6 2.109(4) C1≡N1 1.167(6) C2≡N2 1.171(6) Fe1—N1 1.916(4) Fe2—N2 1.890(4) Fe1—P1 2.203(1) Fe1—P2 2.207(1) Fe2—P3 2.245(1) Fe2—P4 2.250(1) C1—Ru1—C2 177.3(2) N1≡C1—Ru1 178.8(4) N2≡C2—Ru1 174.7(4) C1≡N1—Fe1 174.8(4) C2≡N2—Fe2 176.1(4) Fe1 . . . Ru1 5.135 Fe2 . . . Ru1 5.049 Fe1 . . . Fe2 10.162 trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 Ru1—C1 2.010(6) Ru1—C2 2.037(6) Ru1—N3 2.108(5) Ru1—N4 2.116(5) Ru1—N5 2.110(5) Ru1—N6 2.104(5) C1≡N1 1.157(7) C2≡N2 1.171(7) Fe1—N1 1.907(5) Fe2—N2 1.903(5) Fe1—P1 2.283(2) Fe1—P2 2.283(2) Fe2—P3 2.267(2) Fe2—P4 2.275(2) C1—Ru1—C2 176.1(2) N1≡C1—Ru1 173.8(5) N2≡C2—Ru1 176.4(5) C1≡N1—Fe1 167.2(5) C2≡N2—Fe2 172.4(5) Fe1 . . . Ru1 5.047 Fe2 . . . Ru1 5.068 Fe1 . . . Fe2 10.019 trans-Ru(.sup.tbupy).sub.4(CN).sub.2 Ru1—C1 2.058(2) Ru1—C2 Ru1—N3 2.107(2) Ru1—N4 2.113(2) Ru1—N5 Ru1—N6 C1≡N1 1.154(3) C2≡N2 Fe1—N1 Fe2—N2 Fe1—P1 Fe1—P2 Fe2—P3 Fe2—P4 C1—Ru1—C2 180.0 N1≡C1—Ru1 179.8(2) N2≡C2—Ru1 C1≡N1—Fe1 C2≡N2—Fe2 Fe1 . . . Ru1 Fe2 . . . Ru1 Fe1 . . . Fe2
[0048] X-ray single crystal diffraction analysis shows that the compound trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2 and 3) is a monoclinic system, Centrosymmetric P2.sub.1/cspace group, the compound trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 is an orthorhombic system, centrosymmetric Pbca space group.
[0049] In addition, the compound trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 contains three uncoordinated dichloromethane solvent molecules, the compound trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3 has two uncoordinated isopropanol and one uncoordinated water solvent molecule, trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 has three uncoordinated isopropanol and three acetonitrile solvent molecules.
[0050] It can be seen from Table 2 that the average value of Fe—N bond length in trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6)].sub.2 is 1.929 Å. The average bond length of F—P is 2.201 Å, and the average bond length of Fe—N in trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 is 1.905 Å and Fe—P bond length is 2.227 Å. It can be seen that as the oxidation reaction progresses, the Fe—N bond length decreases, while the Fe—P bond length increases, which shows that trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 are in +2 oxidation state, and trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 are +3 oxidation states, espectively. trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3 has an average of Fe1-P bond length of 2.204 Å, an average of Fe2-P bond length of 2.248 Å, an average of Fe1-N1 bond length of 1.196 Å, The average value Fe2-N2 bond length is 1.890 Å. It can be seen that the Fe1-P bond length is shorter than the Fe2-P bond length, and the Fe1-N1 bond length is longer than the Fe2-N2 bond length. This is because Fe2 has fewer anti-bonds to the phosphine ligand, which shows that the two iron centers in trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3 have different oxidation states Fe1(+2) and Fe2(+3).
[0051] In addition, it can be seen from Table 2 that the compound trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2, 3, 4) The shortest Fe . . . Ru.sup.II distance is 5.0˜5.1 Å, and the shortest Fe . . . Fe distance connected by the diamagnetic cyano metal bridge NC—Ru.sup.II—CN is 10.0˜10.2 Å.
[0052] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 prepared in this example was dissolved in dichloromethane, and then subjected to a cyclic voltammetry test. The cyclic voltammogram of is shown in
[0053] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 prepared in this example was dissolved in acetonitrile, and then subjected to a cyclic voltammetry test. The resulting cycle voltammogram is shown in
[0054] After testing, the cyclic voltammograms of the compound trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2, 3, 4) are all the same The cyclic voltammogram of trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 has two pairs of reversible redox peaks, these two pairs of reversible The redox peak indicates the one-electron oxidation product trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.3 and the two-electron oxidation product trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 are stable and can be separated.
[0055] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2, 3, 4) prepared in Example 1 was analyzed by infrared spectroscopy. The infrared spectrum is shown in
[0056] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2, 3, 4) prepared in this example was dissolved in acetonitrile, and then analyze the electronic absorption spectrum at room temperature, and the obtained electronic absorption spectrum is shown in
[0057] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6]. (n=2,3,4) prepared in this example was subjected to electron paramagnetic resonance at room temperature, EPR spectrum is shown in
[0058] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.2 and trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF6].sub.3 prepared in this example is subjected to a variable temperature magnetic susceptibility test in an external field of 1000 Oe and a temperature range of 2-300K. The resulting variable temperature magnetic susceptibility curve is shown in
[0059] The trans-[Cp(dppe)Fe(NC)Ru(.sup.tbupy).sub.4(CN)Fe(dppe)Cp][PF.sub.6].sub.4 prepared in this example was subjected to variable temperature magnetization in an external field of 1000 Oe and a temperature range of 2-300K Rate test, the obtained variable temperature magnetic susceptibility curve is shown in