The diverse functions of isocyanides in phosphorescent metal complexes

Sutton, Gregory D.; Olumba, Morris E.; Nguyen, Yennie H.; Teets, Thomas S.

doi:10.1039/d1dt03312c

Cited by 28 publications

(30 citation statements)

References 71 publications

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“…However, the calculated spin density distribution in the optimized T 1 state (Figure ) is located mainly on the cyclometalated ligand and to a lesser extent in platinum (Pt, 0.1377 1a , 0.1912 1b , 0.0850 3a ), with a negligible contribution of the other coligands, thus supporting a predominant 3 IL state with 3 MLCT contribution higher in the neutral complexes 1 than in 3 . This result is in coherence with numerous works on cyclometalated isocyanide metal complexes, in which the large separation between the 3 MLCT and 3 IL states lead to a weak configuration interaction and a predominant 3 IL character in T 1 . In agreement with this, the calculated contribution of the Pt center in the SOMO-1 (Figure S26 and Table S11) decreases (Pt 9% 1a , 16% 1b , 3% 3a ) in the optimized T 1 state in relation to the optimized S 0 geometry, especially for 1 (HOMO, 30% 1a , 34% 1b , 5% 3a ), suggesting distortion upon excitation.…”

Section: Photophysical Properties and Theoretical Calculationssupporting

confidence: 89%

“…This result is in coherence with numerous works on cyclometalated isocyanide metal complexes, in which the large separation between the 3 MLCT and 3 IL states lead to a weak configuration interaction and a predominant 3 IL character in T 1 . 26 In agreement with this, the calculated contribution of the Pt center in the SOMO-1 ( Figure S26 and Table S11 ) decreases (Pt 9% 1a , 16% 1b , 3% 3a ) in the optimized T 1 state in relation to the optimized S 0 geometry, especially for 1 (HOMO, 30% 1a , 34% 1b , 5% 3a ), suggesting distortion upon excitation. The calculated emission wavelengths [ 1a (521), 1b (619), 3a (531 nm)] are consistent with the monomer emission observed [ 1a (467), 1b (524), 3a (474 nm), PS 1 wt %], although with expected overestimated values.…”

Section: Photophysical Properties and Theoretical Calculationssupporting

confidence: 74%

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Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Martínez-Junquera

Lalinde

2022

Inorg. Chem.

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Here, we describe the neutral cyclometalated tert- butylisocyanide Pt II complexes, [Pt(C ∧ N)Cl(CNBu t )] 1 , the double salts [Pt(C ∧ N)(CNBu t ) 2 ][Pt(C ∧ N)Cl 2 ] 2 , and the cationic complexes [Pt(C ∧ N)(CNBu t ) 2 ]ClO 4 3 [C∧N = difluorophenylpyridine (dfppy, a ), 4-(2-pyridyl)benzaldehyde (ppy-CHO, b )]. A comparative study of the pseudopolymorphs 1a , 1a·CHCl 3 , 1b , 1b·0.5Toluene , 1b·0.5PhF , and 3a·0.25CH 2 Cl 2 reveals strong aggregation through Pt···Pt and/or π···π stacking interactions to give a variety of distinctive one-dimensional (1D) infinite chains, which modulate the photoluminescent properties. This intermolecular long-range aggregate formation is the main origin of the photoluminescent behavior of 1a and 1b complexes, which exhibit highly sensitive and reversible responses to multiple external stimuli including different volatile organic compounds (VOCs), solvents, temperatures, and pressures, with distinct color and phosphorescent color switching from green to red. Furthermore, complex 1b undergoes supramolecular self-assembly via Pt···Pt and/or π···π interactions into a polymer thin polystyrene (PS) film 10 wt % in response to toluene vapors, and 3a exhibits vapochromic and vapoluminescent behavior. Theoretical simulations on the dimer, trimer, and tetramer models of 1a and 1b have been carried out to get insight into the photophysical properties in the aggregated solid state.

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Section: Photophysical Properties and Theoretical Calculationssupporting

confidence: 89%

Section: Photophysical Properties and Theoretical Calculationssupporting

confidence: 74%

Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Martínez-Junquera

Lalinde

2022

Inorg. Chem.

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“…2 ). 19–21 The collective σ-donating and π-accepting properties of the isocyanide ligands 25 cause a strong ligand field, in which the abovementioned MC states are energetically less accessible than in typical iron( ii ) polypyridines, 26 thereby allowing for emission from the lowest MLCT excited state. The chelating nature of our di- and triisocyanides imparts robustness, and possibly contributes to reducing the efficiency of (undesired) nonradiative excited-state relaxation processes as a consequence of enhanced rigidity.…”

Section: Discussionmentioning

confidence: 99%

Luminescent chromium(0) and manganese(i) complexes

Wegeberg

Wenger

2022

Dalton Trans.

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“…The related molecules supported by the tris(2-pyridyl)borate 3 as well as a copper(I) carbonyl complex of a fluorinated tris(1-pyrazolyl)borate are also presented. The carbonyl and isocyanide complexes were chosen for this study not only because of their importance ,− but also since their CO and CN stretch could serve as a gauge of ligand electronic effects on the metal sites . It is noteworthy that isolable silver carbonyl complexes are also quite rare. ,,− …”

Section: Introductionmentioning

confidence: 99%

Carbonyl and Isocyanide Complexes of Copper and Silver Supported by Fluorinated Poly(pyridyl)borates

Vanga

Noonikara‐Poyil

et al. 2022

Organometallics

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The pyridine-based poly(pyridyl)borates are a recent addition to the scorpionate family. Furthermore, pyridyl ring substituted analogues are also rare. The synthesis of a bis(pyridyl)borate featuring trifluoromethyl substituted pyridyl donor arms and its utility in isocyanide and carbonyl chemistry of copper(I) and silver(I) have been described together with related molecules supported by a fluorinated tris(pyridyl)borate, and a comparison to the better-known poly(pyrazolyl)borate relatives. X-ray crystal structures of copper and silver complexes show that the B-arylated, bis-and tris(pyridyl)borate ligands use only two pyridyl moieties for metal ion coordination. Flanking B-aryl groups close to metal sites are also a common feature in copper and silver complexes supported by [Ph 2 B(6-(CF 3 )Py) 2 ] − and [t-BuC 6 H 4 B(6-(CF 3 )Py) 3 ] − . The CN stretching frequencies of the t-BuNC complexes of Cu(I) and Ag(I) are notably higher than that of the free t-BuNC. The CO stretch of the analogous fluorinated poly(pyridyl)borate ligand supported metal carbonyls lies closer to that of the free CO, indicating the presence of fairly Lewis acidic metal sites. Metal bound carbonyl stretching frequencies of comparable poly(pyridyl)borate and poly(pyrazolyl)borate have been utilized to gauge the relative donor properties of the two ligand families.

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The diverse functions of isocyanides in phosphorescent metal complexes

Abstract: This Perspective describes the diverse roles played by isocyanides in supporting photoluminescent transition metal complexes.

Cited by 28 publications

References 71 publications

Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Luminescent chromium(0) and manganese(i) complexes

Carbonyl and Isocyanide Complexes of Copper and Silver Supported by Fluorinated Poly(pyridyl)borates

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