Fine-Tuning Electronic Properties of Luminescent Pt(II) Complexes via Vertex-Differentiated Coordination of Sterically Invariant Carborane-Based Ligands

Kirlikovali, Kent O.; Axtell, Jonathan C.; Anderson, Kierstyn; Djurovich, Peter I.; Rheingold, Arnold L.; Spokoyny, Alexander M.

doi:10.1021/acs.organomet.8b00475

Cited by 35 publications

(26 citation statements)

References 108 publications

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“…106 Such differences in the κ 2 binding mode of bis(o-carborane) (κ 2 -B,C- vs. κ 2 -C,C-bound) manifest as subtle differences in the electrochemical redox potential and luminescent properties of Pt(II) coordination complexes. 107…”

Section: Discussionmentioning

confidence: 99%

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

2019

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Over the past several decades, metal-catalyzed cross-coupling has emerged as a very powerful strategy to functionalize carbon-based molecules. More recently, some of the cross-coupling methodologies have been adapted to inorganic compounds including boron-rich clusters. The development of this chemistry relies on the ability to synthesize halogenated boron-rich clusters which can serve as electrophilic cross-coupling partners with nucleophilic substrates in the presence of a metal catalyst. While the cross-coupling chemistry with boron-clusters is conceptually reminiscent to that of its hydrocarbon counterparts, several key aspects including the spheroidal bulk of clusters, and the distinct nature of boron-halogen / boron-heteroatom bonds make this chemistry unique. The utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral boranes including neutral and anionic carboranes, metallaboranes, and carbon-free boranes. Importantly, cross-coupling enables a suite of boron-heteroatom (C, N, O, P, S) couplings to prepare boron cluster-based systems that can be used for ligand design, medicinal chemistry, and materials applications.

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Section: Discussionmentioning

confidence: 99%

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

2019

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“…Among them, the icosahedral closo-ortho-carborane (o-C 2 B 10 H 12 ) cluster has recently attracted attention as a prominent functional group with a three-dimensional unit. [12][13][14][15][16][17][18][19][20][21][22][23][24] The strong electron withdrawing property of o-carborane, which originates from the high polarizability of its σaromaticity [25][26][27][28] via the high Lewis acidity of the ten boron atoms in a cluster, is predominantly responsible for its intriguing photophysical properties when the carbon atom in the cluster is substituted with conjugated π-aromatic moieties. [29][30][31][32][33] Such features enable intramolecular charge-transfer (ICT) transitions in the conjugated system, resulting in the formation of electronic donor (D, π-aromatic group)-acceptor (A, o-carborane) dyad complexes.…”

Section: Introductionmentioning

confidence: 99%

Naphthyl‐ and Quinoline‐Appended o‐Carboranyl Luminophores: Intramolecular Charge Transfer‐Based Radiative Decay Controlled by Structural Geometry around C−C Bond Axis

Ryu

Lee

et al. 2021

Eur J Inorg Chem

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Naphthyl-and quinoline-appended o-carboranyl compounds, NCB and QCB, respectively, were prepared and characterized by multinuclear nuclear magnetic resonance spectroscopy, elemental analysis, and single crystal X-ray diffraction. Although both the compounds were non-emissive in the solution state at 298 K, they were photoluminescent in the rigid state (in THF at 77 K and film state) in the region 450-550 nm. Theoretical calculation of the optimized structure in the S 1 state suggested that the low-energy emissive bands for NCB and QCB were attributed to intramolecular charge transfer (ICT) transition. Intriguingly, the CÀ C bond axis of the o-carborane in NCB in the solid state was more orthogonal to the plane of the appended aromatic group than that in QCB, indicating relatively high delocalization between the o-carborane and aromatic moieties of NCB. The quantum efficiency and radiative decay constant of the ICT-based emission of NCB in the film state were much higher than those of QCB. These findings imply that the structural geometry around the CÀ C bond axis of the ocarborane is a decisive factor in accelerating the ICT-based radiative decay in the o-carbonyl luminophores in the rigid state.

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“…Since the discovery of bis(carboranes) in 1964, the chemistry of 1,1 -bis(o-carborane) (Scheme 1, a) has evolved rapidly, particularly once a high-yielding synthetic route was devised in 2003. Bis(carborane) offers a versatile building block in designing threedimensional molecules, an array of homogeneous catalyst precursors, luminescent materials and organic derivatives via C cage -H or B cage -H functionalisation [1][2][3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)

Mandal

Rosair

2020

Crystals

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The metalation of [Tl]2[1-(1′-3′,1′,2′-closo-TlC2B9H10)-3,1,2-closo-TlC2B9H10], with the smaller {Ni(dmpe)} fragment sourced from [Ni(dmpe)Cl2], is explored. The bis(metalated) products are obtained as a diastereoisomeric mixture. These isomers were separated, fully characterised spectroscopically and crystallographically and identified as rac-[1-(1′-3′-(dmpe)-3′,1′,2′-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10] (1) and meso-[1-(1′-3′-(dmpe)-3′,1′,2′-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10] (2). Previously, these 3,1,2-NiC2B9-3′,1′,2′-NiC2B9 architectures (where both cages are not isomerised), were inaccessible, and thus new structures can be achieved during bis(nickelation) with {Ni(dmpe)}. Further, the metalation of the tetra-thallium salt with the bulky {Ni(dppe)} fragment sourced from [Ni(dppe)Cl2] was also studied. These bis(nickelated) products were also fully characterised and are afforded as the stereospecific species rac-[1-(1′-3′-(dppe)-3′,1′,2′-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10] (3) and [1-(2′-4′-(dppe)-4′,1′,2′-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10] (4α). In the latter metalation, compound 3 shows intramolecular dihydrogen bonding, contributing to the stereospecificity, whereas isomerisation from 3,1,2 to 4,1,2- in the 4α is related to steric relief.

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Fine-Tuning Electronic Properties of Luminescent Pt(II) Complexes via Vertex-Differentiated Coordination of Sterically Invariant Carborane-Based Ligands

Cited by 35 publications

References 108 publications

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

Naphthyl‐ and Quinoline‐Appended o‐Carboranyl Luminophores: Intramolecular Charge Transfer‐Based Radiative Decay Controlled by Structural Geometry around C−C Bond Axis

Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)

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