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Multielectron Redox Chemistry of a Neutral, NIR‐Active, Indigo‐Pillared Re I ‐Based Triangular Metalloprism
Author(s) -
Bhattacharya Dibyendu,
Chang CheHao,
Cheng YuHsiang,
Lai LongLi,
Lu HsiuYu,
Lin ChingYao,
Lu KuangLieh
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201102087
Subject(s) - chemistry , homo/lumo , unpaired electron , electron paramagnetic resonance , crystallography , redox , cyclic voltammetry , molecule , photochemistry , indigo , solvatochromism , ligand (biochemistry) , quantum yield , electrochemistry , inorganic chemistry , organic chemistry , electrode , fluorescence , art , visual arts , physics , receptor , biochemistry , nuclear magnetic resonance , quantum mechanics
Self‐assembled, hexarhenium(I), triangular metalloprism compound [{(CO) 3 Re(μ‐ 2 )Re(CO) 3 } 3 (μ 3 ‐ 1 ) 2 ] ( 3 ) featuring three bis‐chelating pillarlike indigo dianions (μ‐ 2 ), each of which connects two fac ‐Re(CO) 3 cores, which are interconnected by a tritopic N donor, that is, a 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine (μ 3 ‐ 1 , tPyTz) ligand, has been synthesized in high yield and characterized. Metalloprism 3 exhibits a strong absorption in the near‐infrared (NIR) region. The reversible, multielectron redox properties of the electrogenerated 3 n species, where n =3+, 0, 3−, 4−, 5−, 8−, in the visible and especially in the NIR region were investigated in THF solution by cyclic voltammetry (CV), chronocoulometry, EPR spectroscopy, and thin‐layer UV/Vis/NIR spectroelectrochemistry (SEC). Stepwise, site‐specific electrochemical reductions lead to the formation of a series of highly stable ion (radical) species in which electrons associated with μ‐ 2 or μ 3 ‐ 1 components of the molecule can be clearly distinguished. An EPR investigation revealed interaction of unpaired electrons with the metal nuclei ( 185,187 Re, I =5/2) in the reduced intermediates. The framework has C 2 symmetry, and accidental degeneracies suffice. Detailed theoretical calculations by structure‐based DFT confirm that the triply degenerate HOMO has ≥70 % indigo character with a sizable dπ‐Re character, while the LUMO is dominated by the triply degenerate indigo ligands, and the LUMO+1 by doubly degenerate tPyTz ligands. A comparison of 3 and previously reported 2,2′‐bis‐benzimidazolate‐ (BiBzlm) or alkoxy‐pillared Re I metalloprisms indicates a very low switching potential with a potential window of less than 1 V and reversibly accessible optical properties with higher stability of the intermediates. The properties exhibited by 3 appear to be due to the slight tuning of the bridging ligand from N,N − to N,O − .