Two molecule-bridged bis(tetracyanoiron) complexes [(NC)(4)Fe(BL)Fe(CN)(4)](n)()(-), BL = 2,2'-bipyrimidine (bpym) and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), were studied by EPR, UV/vis/near-IR and IR spectroelectrochemistry (n = 2-5) in aprotic media. Following these results, the Fe(2)(2.5) formulation is the correct valence description for the metal centers in the bptz-bridged trianion (K(c) = 10(14.6) in CH(3)CN), whereas the localized Fe(III)/Fe(II) formulation is appropriate for the bpym-bridged system (K(c) = 10(5.4) in CH(3)CN and 10(6.4) in CH(2)Cl(2)). In contrast to common perception, the larger tetrazine-bridged system with the longer metal-metal distance exhibits much stronger metal-metal coupling than the bpym-bridged analogue, a consequence of the very low lying pi LUMO of tetrazines with high MO coefficients at the coordinating nitrogen centers.
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Institute of Pharmaceutical Research, GLA University, Mathura, India.
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Front Public Health
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Department of Epidemiology and Biostatistics, School of Public Health, Anhui Medical University, Hefei, China.
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National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, 100021, People's Republic of China.
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Chem Sci
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Yusuf Hamied Department of Chemistry, University of Cambridge Lensfield Road Cambridge CB2 1EW UK
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