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

Understanding the relationship between molecular design and packing modes constitutes one of the major challenges in self‐assembly and is essential for the preparation of functional materials. Herein, we have achieved high precision control over the supramolecular packing of amphiphilic PtII complexes by systematic variation of the hydrophilic side‐chain length. A novel approach of general applicability based on complementary X‐ray diffraction and solid‐state NMR spectroscopy has allowed us to establish a clear correlation between molecular features and supramolecular ordering. Systematically increasing the side‐chain length gradually increases the steric demand and reduces the extent of aromatic interactions, thereby inducing a gradual shift in the molecular packing from parallel to a long‐slipped organization. Notably, our findings highlight the necessity of advanced solid‐state NMR techniques to gain structural information for supramolecular systems where single‐crystal growth is not possible. Our work further demonstrates a new molecular design strategy to modulate aromatic interaction strengths and packing arrangements that could be useful for the engineering of functional materials based on PtII and aromatic molecules.

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Tuning the Molecular Packing of Self‐Assembled Amphiphilic Pt^II Complexes by Varying the Hydrophilic Side‐Chain Length

Herkert

Selter

Daniliuc

et al. 2021

Chemistry A European J

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Variations in the Solid‐State Emissions of Clothespin‐Shaped Binuclear trans‐Bis(salicylaldiminato)platinum(II) with Halogen Functionalities

Ikeshita

Ito

2019

Eur J Inorg Chem

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The syntheses, aggregation motifs and solid-state emissions of clothespin-shaped binuclear trans-bis(salicylaldiminato)platinum(II) complexes 1-4 bearing halogen atoms (X) at the para positions of phenoxy moieties are described and compared with those of the non-substituted analog 5. Crystalline (±)-4 (X = I, polymorph B) obtained by recrystallization from benzene exhibits intense phosphorescent emission under UV irradiation at ambient temperature, while crystals of (±)-1 (X = F), (±)-2 (X = Cl), (±)-3 (X = Br) and (±)-4 (X = I, polymorph A), obtained from poor solvents including hexanes, are less emissive under the same conditions. The emission intensities of these crystals increase in the order of (±)-4 (B) > (±)-5 > (±)-1- [a] 3562 platinum(II) complexes bearing halogen functionalities, with a focus on a mechanistic rationale for the specific emission enhancements observed.Scheme 2. Clothespin-shaped platinum(II) complexes 1-5 (R-form).

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

Cited by 4 publications

References 114 publications

Tuning the Molecular Packing of Self‐Assembled Amphiphilic Pt^II Complexes by Varying the Hydrophilic Side‐Chain Length

Tuning the Molecular Packing of Self‐Assembled Amphiphilic Pt^II Complexes by Varying the Hydrophilic Side‐Chain Length

Variations in the Solid‐State Emissions of Clothespin‐Shaped Binuclear trans‐Bis(salicylaldiminato)platinum(II) with Halogen Functionalities

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

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

Cited by 4 publications

References 114 publications

Tuning the Molecular Packing of Self‐Assembled Amphiphilic PtII Complexes by Varying the Hydrophilic Side‐Chain Length

Tuning the Molecular Packing of Self‐Assembled Amphiphilic PtII Complexes by Varying the Hydrophilic Side‐Chain Length

Variations in the Solid‐State Emissions of Clothespin‐Shaped Binuclear trans‐Bis(salicylaldiminato)platinum(II) with Halogen Functionalities

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

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Product

Resources

About

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

Tuning the Molecular Packing of Self‐Assembled Amphiphilic Pt^II Complexes by Varying the Hydrophilic Side‐Chain Length

Tuning the Molecular Packing of Self‐Assembled Amphiphilic Pt^II Complexes by Varying the Hydrophilic Side‐Chain Length