B(III)-subporphyrazines, B(III)-subporphyrins and their hybrids

“…This templated cyclotrimerization also encompasses mixed cyclotrimerization (also referred to as statistical cross-condensation or cocyclization) of two different o -dinitrile precursors to access new diiminoisoindole-hybridized analogues with fundamentally different physicochemical properties. Mixed cyclotrimerization typically forms hybrid BsubPc macrocycles with lower molecular symmetry (e.g., C s symmetry) and altered spectroscopic properties. ,− This approach has been further applied for the preparation of π-extended BsubPc hybrids with two-oxygen-bridged aromatic fragments, pyrene-fused diiminoisoindole units, core-expanded inner pyrrolic rings, − and benzo-annulated units. − …”

Section: Introductionmentioning

confidence: 99%

Bulking Up the Bay-Position Substituents Enables Enhanced Selectivity of C_s-Symmetric Boron Subphthalocyanine–Subnaphthalocyanine Hybrids

Farac,

Lough,

Bender

2024

Precision Chemistry

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The precise synthesis of subporphyrinoid hybrids with π-expanded topologies and unique material properties plays a promising role in the design of functional macrocycles. Easy, selective, and controllable routes to boron subphthalocyanine− subnaphthalocyanine hybrids, Bsub(Pc 3-p -Nc p )s, are desirable for this purpose yet synthetically challenging due to random mixtures of C s -, C 3v -, and, in some cases, C 1 -symmetric compounds that form during traditional statistical mixed cyclotrimerizations. Herein, we addressed this issue by developing a sterically driven mixed cyclotrimerization with enhanced selectivity for the targeted C s -symmetric hybrid and complete suppression of sterically crowded macrocyclic byproducts. This process, coupled with a rationally designed precursor bearing bulky phenyl substituents, enabled the synthesis and characterization of bay-position phenylated Ph 2 -(R p ) 8 Bsub(Pc 2 -Nc 1 ) hybrids with halogens (R p = Cl or F) in their peripheral isoindole rings. Reaction selectivity ranged between 59 and 72% with remarkable yields, significantly higher than that of conventional mixed cyclotrimerizations. These findings were augmented by theoretical calculations on precursor Lewis basicity as guiding principles into hybrid macrocycle formation. Additionally, the incorporation of unfused phenyl groups and halogen atoms into the hybrid framework resulted in fine-tuned optical, structural, electronic, and electrochemical properties. This straightforward approach achieved improved selectivity and controlled narrowing of the product distribution, affording the efficient synthesis of structurally sophisticated Bsub(Pc 2 -Nc 1 ) hybrids. This then expands the library of 3-dimensional π-extended macrocycles for use in a range of applications, such as in optoelectronic devices with precisely tailored optical properties.

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“…Various meso-substituted subporphyrin derivatives have been synthesized [2][3][4] and were promising functional materials due to their tunable optical and electronic properties, high fluorescence quantum yields, and large nonlinear optical (NLO) responses. [5][6][7] The optical and electronic properties of subporphyrins are significantly disturbed by the meso-substituents, and thus functionalization of the meso-positions is a feasible way to tune these properties. A variety of novel compounds based on a subporphyrin (SubP) as an electron donor and naphthyldiimide (NDI) as an acceptor were synthesized and studied by time-resolved emission and transient absorption measurements.…”

Section: Introductionmentioning

confidence: 99%

Electronic and Nonlinear Optical Properties of B(III)‐Submonoazaporphyrin‐π‐Diimide Compounds: A Density Functional Theory Study

Liu,

Hou

2024

ChemPhysChem

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Three hypothetical complexes were designed using diimides (PMDI, NTCDI and PTCDI) as the acceptor unit and B(III)‐submonoazaporphyrin (1) as the donor unit. These complexes have smaller HOMO‐LUMO energy gaps (3.39‐3.96 eV) than pristine 1 (6.61 eV). Further, the energy gap can be tuned by changing the number of benzene rings of these diimides. Remarkably, these proposed complexes possess considerable first hyperpolarizabilities (β0) (4865‐6921 a.u.), and the regularity of the β0 values remained the same in the gas phase and toluene solvent conditions. There is an inverse relationship between the energy gap and the polarizability/first hyperpolarizability. In addition, absorption spectra, frontier molecular orbitals, and hole electron distributions were obtained using time‐dependent density functional theory calculations to emphasize the relationship between structure and properties. Ultraviolet‐Visible absorption spectra reveals that all complexes show satisfying IR working regions. Further analysis of the first hyperpolarizability density reveals the nature of the excellent NLO properties of the studied systems. This study can provide valuable insights for the development of potential high‐performance NLO molecules.

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B(III)-subporphyrazines, B(III)-subporphyrins and their hybrids

Cited by 9 publications

References 162 publications

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

Bulking Up the Bay-Position Substituents Enables Enhanced Selectivity of C_s-Symmetric Boron Subphthalocyanine–Subnaphthalocyanine Hybrids

Electronic and Nonlinear Optical Properties of B(III)‐Submonoazaporphyrin‐π‐Diimide Compounds: A Density Functional Theory Study

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B(III)-subporphyrazines, B(III)-subporphyrins and their hybrids

Cited by 9 publications

References 162 publications

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

Bulking Up the Bay-Position Substituents Enables Enhanced Selectivity of Cs-Symmetric Boron Subphthalocyanine–Subnaphthalocyanine Hybrids

Electronic and Nonlinear Optical Properties of B(III)‐Submonoazaporphyrin‐π‐Diimide Compounds: A Density Functional Theory Study

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Bulking Up the Bay-Position Substituents Enables Enhanced Selectivity of C_s-Symmetric Boron Subphthalocyanine–Subnaphthalocyanine Hybrids