Four‐Center Oxidation State Combinations and Near‐Infrared Absorption in [Ru(pap)(Q)2]n (Q=3,5‐Di‐tert‐butyl‐N‐aryl‐1,2‐benzoquinonemonoimine,pap=2‐Phenylazopyridine) |
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| Authors: | Dr. Dipanwita Das Hemlata Agarwala Dr. Abhishek Dutta Chowdhury Tuhin Patra Dr. Shaikh M. Mobin Prof. Dr. Biprajit Sarkar Prof. Dr. Wolfgang Kaim Prof. Dr. Goutam Kumar Lahiri |
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| Affiliation: | 1. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai‐400076 (India);2. Institut für Anorganische Chemie, Universit?t Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart (Germany) |
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| Abstract: | The complex series [Ru(pap)(Q)2]n ([ 1 ]n–[ 4 ]n; n=+2, +1, 0, ?1, ?2) contains four redox non‐innocent entities: one ruthenium ion, 2‐phenylazopyridine (pap), and two o‐iminoquinone moieties, Q=3,5‐di‐tert‐butyl‐N‐aryl‐1,2‐benzoquinonemonoimine (aryl=C6H5 ( 1+ ); m‐(Cl)2C6H3 ( 2+ ); m‐(OCH3)2C6H3 ( 3+ ); m‐(tBu)2C6H3 ( 4 +)). A crystal structure determination of the representative compound, [ 1 ]ClO4, established the crystallization of the ctt‐isomeric form, that is, cis and trans with respect to the mutual orientations of O and N donors of two Q ligands, and the coordinating azo N atom trans to the O donor of Q. The sensitive C? O (average: 1.299(3) Å), C? N (average: 1.346(4) Å) and intra‐ring C? C (meta; average: 1.373(4) Å) bond lengths of the coordinated iminoquinone moieties in corroboration with the N?N length (1.292(3) Å) of pap in 1 + establish [RuIII(pap0)(Q.?)2]+ as the most appropriate electronic structural form. The coupling of three spins from one low‐spin ruthenium(III) (t2g5) and two Q.? radicals in 1 +– 4 + gives a ground state with one unpaired electron on Q.?, as evident from g=1.995 radical‐type EPR signals for 1 +– 4 +. Accordingly, the DFT‐calculated Mulliken spin densities of 1 + (1.152 for two Q, Ru: ?0.179, pap: 0.031) confirm Q‐based spin. Complex ions 1 +– 4 + exhibit two near‐IR absorption bands at about λ=2000 and 920 nm in addition to intense multiple transitions covering the visible to UV regions; compounds [ 1 ]ClO4–[ 4 ]ClO4 undergo one oxidation and three separate reduction processes within ±2.0 V versus SCE. The crystal structure of the neutral (one‐electron reduced) state ( 2 ) was determined to show metal‐based reduction and an EPR signal at g=1.996. The electronic transitions of the complexes 1 n– 4 n (n=+2, +1, 0, ?1, ?2) in the UV, visible, and NIR regions, as determined by using spectroelectrochemistry, have been analyzed by TD‐DFT calculations and reveal significant low‐energy absorbance (λmax>1000 nm) for cations, anions, and neutral forms. The experimental studies in combination with DFT calculations suggest the dominant valence configurations of 1 n– 4 n in the accessible redox states to be [RuIII(pap0)(Q.?)(Q0)]2+ ( 1 2+– 4 2+)→[RuIII(pap0)(Q.?)2]+ ( 1 +– 4 +)→[RuII(pap0)(Q.?)2] ( 1 – 4 )→[RuII(pap.?)(Q.?)2]? ( 1 ?– 4 ?)→[RuIII(pap.?)(Q2?)2]2? ( 1 2?– 4 2?). |
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| Keywords: | density functional calculations electronic structure non‐innocent ligands ruthenium spectroelectrochemistry structure elucidation |
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