Variations in the emission of polymethylene-vaulted trans-bis(salicylaldiminato)platinum(II) complexes incorporating methoxy functionalities with linkage length and substitution position

Komiya, Naruyoshi; Okada, Minoru; Inoue, Ryo; Kawamorita, Soichiro

doi:10.1016/j.poly.2015.05.035

Cited by 10 publications

(1 citation statement)

References 63 publications

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“…11a,c Organometallic complexes with chiral ligands have attracted increasing attention in recent years as promising CPL materials owing to their large Stokes shifts and highly efficient phosphorescence properties, which are difficult to achieve using SOMs. 15 Various examples of CPL-active organometallic complexes whose metal centers are Cr(III), 16 Zn(II), 17 Cu(I), 18 Ru(III), 19 Re(I), 20 Pt(II), 21 Ir(III), 22 and Au(I) 23 have been used for developing efficient CPL emitters. However, despite several studies on the correlation between the structure and CPL properties in SOMs, 11b,14d,f,g a clear molecular design for achieving efficient CPL has not been established for organo-metallic complexes.…”

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confidence: 99%

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1′-Binaphthyl Frameworks

2023

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In this study, the synthesis, structure, and chiroptical response control of planar chiral polymethylene-vaulted trans-bis [(β-iminomethyl)aryloxy]platinum(II) complexes bearing axially chiral 1,1′-binaphthyl ligands are described. A series of enantiopure polymethylene (n = 4−10)-vaulted complexes were prepared in 6 steps using commercially available (R)-or (S)-BINOL as the starting material without an optical resolution process. The trans-coordination and three-dimensional vaulted structures of the platinum complexes were elucidated from X-ray diffraction (XRD) studies. The complexes were found to show structural dependence of chiroptical responses in the dilute solution state such that the absolute values of [α] D , dissymmetry factors g abs in circular dichroism (CD), and g lum in circularly polarized luminescence (CPL) increased upon shortening the length of the polymethylene bridges. The enhanced chiroptical responses were theoretically investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, and the results are discussed in terms of the molecular structures and transition dipole moments of the ground states. The structural dependence of the chiroptical responses was ascribed to the distortion of the coordination platforms caused by restriction of the vaulting methylene linkers.

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Section: ■ Introductionmentioning

confidence: 99%

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1′-Binaphthyl Frameworks

2023

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Heat‐Resistant Properties in the Phosphorescence of trans‐Bis[β‐(iminomethyl)aryloxy]platinum(II) Complexes: Effect of Aromaticity on d–π Conjugation Platforms

Inoue

Naito

Ehara

2019

Chemistry A European J

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The heat‐resistant properties towards thermal emission quenching of trans‐bis[(β‐iminomethyl)aryloxy]platinum(II) complexes bearing 3‐iminomethyl‐2‐naphtholato‐ (1), 1‐iminomethyl‐2‐naphtholato‐ (2), 2‐iminomethyl‐1‐naphtholato‐ (3), and 2‐iminomethyl‐1‐phenolato (4) moieties, and a mechanistic rationale of these properties, are described in this report. Complex 1 a, with N,N′‐dipentyl groups, exhibits intense red emission in 2‐methyl‐2,3,4,5‐tetrahydrofuran (2‐MeTHF) at 298 K, whereas the analogues 2 a–4 a are less or non‐emissive under the same measurement conditions. All four complexes are highly emissive at 77 K. The heat‐resistant properties toward thermal emission quenching (Φ298 K/Φ77 K) increase in the order 1 a (0.52)>2 a (0.09)>3 a (0.02)>>4 a (0.00). We investigated the emission decay and thermal‐deactivation processes using density functional theory (DFT), time‐dependent (TD) DFT, and double‐hybrid density functional theory (DHDF) calculations of N,N′‐diethyl forms 1 b–4 b, and discuss the results with a focus on the energy levels, molecular structures, and electronic configurations in the triplet excited states. The energy differences between the triplet metal–ligand charge transfer (3MLCT) state and minimum‐energy crossing point between the lowest triplet state and singlet ground state (MECP) increase in the order 1 a>2 a, 3 a>4 a, consistent with the experimental results for the heat‐resistant properties of these complexes. The origin of the present structure dependence of the 3MLCT–MECP energy gap is ascribed to the ease or difficulty of the high‐lying dσ* orbital participating in the MECP upon thermal structural distortion. The structure dependence in energy gaps between the π* and dσ* orbitals, which is key for facilitating the thermal deactivation process, is rationally correlated with the extent of aromaticity on the coordination platforms (1 b>(2 b, 3 b)>4 b).

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Regiospecific Remote Pt–H Interactions in Oligomethylene‐Vaulted (N^{^}C^{^}N)‐Pincer Pt^II Complexes

et al. 2018

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(N^C^N)‐Pincer type bis(iminomethyl)phenylPtII complexes 1 and 2 having a macrocyclic vaulting structure consisting of deca‐ undeca‐, and dodecamethylene bridges were synthesized and subsequently characterized by NMR, IR spectroscopy, mass spectrometry, and single‐crystal XRD. Unprecedented remote intramolecular Pt–H interactions were observed on the linker hydrogen atoms at β‐and ζ‐positions in a highly regiospecific manner both in the crystal and solution states. The hydrogen bonding nature, originating from overlap between Pt dz² and σ* of the specific C–H bonds, was revealed by NBO analysis of 1 on the basis of dispersion‐corrected DFT calculations.

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Variations in the emission of polymethylene-vaulted trans-bis(salicylaldiminato)platinum(II) complexes incorporating methoxy functionalities with linkage length and substitution position

Cited by 10 publications

References 63 publications

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1′-Binaphthyl Frameworks

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1′-Binaphthyl Frameworks

Heat‐Resistant Properties in the Phosphorescence of trans‐Bis[β‐(iminomethyl)aryloxy]platinum(II) Complexes: Effect of Aromaticity on d–π Conjugation Platforms

Regiospecific Remote Pt–H Interactions in Oligomethylene‐Vaulted (N^{^}C^{^}N)‐Pincer Pt^II Complexes

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Variations in the emission of polymethylene-vaulted trans-bis(salicylaldiminato)platinum(II) complexes incorporating methoxy functionalities with linkage length and substitution position

Cited by 10 publications

References 63 publications

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1′-Binaphthyl Frameworks

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1′-Binaphthyl Frameworks

Heat‐Resistant Properties in the Phosphorescence of trans‐Bis[β‐(iminomethyl)aryloxy]platinum(II) Complexes: Effect of Aromaticity on d–π Conjugation Platforms

Regiospecific Remote Pt–H Interactions in Oligomethylene‐Vaulted (N^C^N)‐Pincer PtII Complexes

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Regiospecific Remote Pt–H Interactions in Oligomethylene‐Vaulted (N^{^}C^{^}N)‐Pincer Pt^II Complexes