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Dalton Trans. 2014 Oct 7;43(37):13932-47. doi: 10.1039/c4dt01821d. Epub 2014 Aug 12.

Electronic structures and selective fluoride sensing features of Os(bpy)2(HL(2-)) and [{Os(bpy)2}2(μ-HL(2-))](2+) (H3L: 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid).

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Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India.


The article deals with the newly designed mononuclear and asymmetric dinuclear osmium(ii) complexes Os(II)(bpy)2(HL(2-)) (1) and [(bpy)2Os(II)(μ-HL(2-))Os(II)(bpy)2](Cl)2 ([2](Cl)2)/[(bpy)2Os(II)(μ-HL(2-))Os(II)(bpy)2](ClO4)2 ([2](ClO4)2), respectively, (H3L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid and bpy = 2,2'-bipyridine). The identity of 1 has been established by its single crystal X-ray structure. The ligand (HL(2-))-based primary oxidation process (E, 0.23 V versus SCE) along with the partial metal contribution (∼20%) in 1 has been revealed by the ligand-dominated HOMO of 1 (HL(2-): 88%, Os: 8%), as well as by the Mulliken spin density distribution of 1(+) (HL(2-): 0.878, Os: 0.220). Accordingly, 1(+) exhibits a free radical type EPR at 77 K with a partial metal-based anisotropic feature (g1 = 2.127, g2 = 2.096, g3 = 2.046; <g> = 2.089; Δg = 0.08). (1)H-NMR of the dinuclear 2(2+) in CDCl3 suggests an intimate mixture of two diastereomeric forms in a 1 : 1 ratio. The DFT-supported predominantly Os(ii)/Os(iii)-based couples of asymmetric 2(2+) at 0.24 V and 0.50 V versus SCE result in a comproportionation constant (Kc) value of 8.2 × 10(4). The class I mixed valent state of 2(3+) (S = 1/2) has, however, been corroborated by the Mulliken spin density distribution of Os1: 0.887, Os2: 0.005, HL(2-): 0.117, as well as by the absence of a low-energy IVCT (intervalence charge transfer) band in the near-IR region (up to 2000 nm). The appreciable spin accumulation on the bridge in 2(3+) or 2(4+) (S = 1, Os1: 0.915, Os2: 0.811 and HL(2-): 0.275) implies a mixed electronic structural form of [(bpy)2Os(III)(μ-HL(2-))Os(II)(bpy)2](3+)(major)/[(bpy)2Os(II)(μ-HL˙(-))Os(II)(bpy)2](3+)(minor) or [(bpy)2Os(III)(μ-HL(2-))Os(III)(bpy)2](4+)(major)/[(bpy)2Os(III)(μ-HL˙(-))Os(II)(bpy)2](4+) (minor), respectively. The mixed valent {Os(III)(μ-HL(2-))Os(II)} state in 2(3+), however, fails to show EPR at 77 K due to the rapid spin relaxation process. The DFT-supported bpy-based two reductions for both 1(+) and 2(2+) appear in the potential range of -1.5 V to -1.8 V versus SCE. The electronic transitions in 1(n) and 2(n) are assigned by the TD-DFT calculations. Furthermore, the potential anion sensing features of 1 and 2(2+)via the involvement of the available N-H proton in the framework of coordinated HL(2-) have been evaluated by different experimental investigations, in conjunction with the DFT calculations, using a wide variety of anions such as F(-), Cl(-), Br(-), I(-), OAc(-), SCN(-), HSO4(-) and H2PO4(-). This, however, establishes that both 1 and 2(2+) are equally efficient in recognising the F(-) ion selectively, with log K values of 6.83 and 5.89, respectively.

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