Cubic Nanogrids for Counterbalance Contradiction among Reorganization Energy, Strain Energy, and Wide Bandgap

Abstract

Molecular cross-scale gridization and polygridization of organic πbackbones make it possible to install 0/1/2/3-dimensional organic wide-bandgap semiconductors (OWBGSs) with potentially ZnO-like fascinating multifunctionality such as optoelectronic and piezoelectronic features. However, gridization effects are limited to uncover, because the establishment of gridochemistry still requires a long time, which offers a chance to understand the effects with a theoretical method, together with data statistics and machine learning. Herein, we demonstrate a state-ofthe-art 3D cubic nanogridon with a size of ∼2 × 2 × 1.5 nm 3 to examine its multigridization of π-segments on the bandgap, molecular strain energy (MSE), as well as reorganization energy (ROE). A cubic gridon (CG) consists of a four-armed bifluorene skeleton and a thiophene-containing fused arene plane with the Csp 3 spirolinkage, which can be deinstalled into face-on or edge-on monogrids. As a result, multigridization does not significantly reduce bandgaps (E g ≥ 4.03 eV), while the MSE increases gradually from 4.72 to 23.83 kcal/mol. Very importantly, the ROE of a CG exhibits an extreme reduction down to ∼28 meV (λ + ) that is near the thermal fluctuation energy (∼26 meV). Our multigridization results break through the limitation of the basic positively proportional relationship between reorganization energies and bandgaps in organic semiconductors. Furthermore, multigridization makes it possible to keep the ROE small under the condition of a high MSE in OWBGS that will guide the cross-scale design of multifunctional OWBGSs with both inorganics' optoelectronic performance and organics' mechanical flexibility.

One‐Pot Synthesis and Excited‐State Dynamics of Null Exciton‐Coupled Diketopyrrolopyrroles Oligo‐Grids

“…[32][33][34][35] In this work, we utilize a novel grid structure to transform thienyl(3,6-di(5-phenylthiophen-2-yl)pyrrolo(3,4-c)pyrrole-1,4(2H,5H)-dione (TDPP-Ref), which has been reported to exhibit SF and TTA-UC in solid state or solution, into covalently ordered nanogrids architectures. [36][37][38][39][40] Nanogrids represent a class of closed-loop molecular building blocks that are created through covalently linking diarylfluorenes. These building blocks are designed with an emphasis on the spatial arrangement, multi-resistance integration, and photoelectric properties of wide-bandgap semiconductors.…”

Electric-Field Effects on the Internal Charge Reorganization Energies of Crystalline Organic Semiconductors

“…Small-molecule organic semiconductors (SMOS) with salient charge-transport (CT) efficiencies are candidate materials for organic field-effect transistors, − organic solar cells, , etc. − According to the semiclassical Marcus theory, in silico predictions or diagnoses of CT efficiencies in SMOS require the accurate computation of CT parameters, for instance, the transfer integral ( t ) and the internal charge reorganization energy (λ). Along with the recent advances on the computation of t that well addresses the electromechanical response and the anisotropy of the measured carrier mobility for SMOS, increasing focus has also been placed on the assessment of λ, − which influences the upper bound of the carrier mobility and is extensively used for novel SMOS design. − …”