On-Surface Boronation of Porphyrin into a Molecular Dipole

TY - JOUR

T1 - On-Surface Boronation of Porphyrin into a Molecular Dipole

AU - Chen, Yanghan

AU - Yi, Wei

AU - Sun, Ye

AU - Kantorovich, Lev

AU - Yu, Miao

N1 - Publisher Copyright: © 2024 American Chemical Society.

PY - 2024/10/9

Y1 - 2024/10/9

N2 - Functionalized porphyrins by introducing exotic atoms into their central cavities have significant applications across various fields. As unique nanographenes, porphyrins functionalized with monoboron are intriguing, yet their synthesis remains highly challenging. Herein, we present the first on-surface boronation of porphyrin, bonding a single boron atom into the porphyrin’s cavity. The boronation is selective, being observed exclusively in molecules featuring a specific aromatic ring-fused structure (ARFS*), not the pristine porphyrin molecule or its other ARFS forms. The boron’s bonding geometry is noncentered, transforming the boronated porphyrin into a molecular dipole and imparting a markedly varied electronic structure. Well-ordered two-dimensional dipole arrays are achieved. Upon elevated thermoactivation, intermolecular O–B–O bonds provide robustness and flexibility to the molecular chains. This work demonstrates the high selectivity of on-surface porphyrin boronation and provides an effective strategy for tailoring molecules’ electronic structure, producing molecular dipoles, and promoting the robustness and flexibility of molecular chains.

AB - Functionalized porphyrins by introducing exotic atoms into their central cavities have significant applications across various fields. As unique nanographenes, porphyrins functionalized with monoboron are intriguing, yet their synthesis remains highly challenging. Herein, we present the first on-surface boronation of porphyrin, bonding a single boron atom into the porphyrin’s cavity. The boronation is selective, being observed exclusively in molecules featuring a specific aromatic ring-fused structure (ARFS*), not the pristine porphyrin molecule or its other ARFS forms. The boron’s bonding geometry is noncentered, transforming the boronated porphyrin into a molecular dipole and imparting a markedly varied electronic structure. Well-ordered two-dimensional dipole arrays are achieved. Upon elevated thermoactivation, intermolecular O–B–O bonds provide robustness and flexibility to the molecular chains. This work demonstrates the high selectivity of on-surface porphyrin boronation and provides an effective strategy for tailoring molecules’ electronic structure, producing molecular dipoles, and promoting the robustness and flexibility of molecular chains.

KW - electronic structure

KW - functionalized porphyrin

KW - on-surface synthesis

KW - scanning tunneling microscopy

KW - selective boronation

UR - https://www.scopus.com/pages/publications/85205794311

U2 - 10.1021/acs.nanolett.4c03456

DO - 10.1021/acs.nanolett.4c03456

M3 - Article

C2 - 39349980

AN - SCOPUS:85205794311

SN - 1530-6984

VL - 24

SP - 12522

EP - 12528

JO - Nano Letters

JF - Nano Letters

IS - 40

ER -