Electronic and Kinetic Feasibility of a 3,6,9,12-Connected Rectangular Chrysene Network for Pt-Assisted Hydrogen Evolution: A Conditional Comparison with a Dibenzochrysene Kagome Benchmark

Abstract

A dibenzo[g,p]chrysene-based, sp2-carbon-linked covalent organic framework provides experimental precedent for visible-light hydrogen evolution under platinum-assisted, sacrificial-donor conditions. That result does not establish whether a network formed from 3,6,9,12-functionalized chrysene nodes will inherit the necessary optical, charge-separation, transport, and redox properties. We formulate a falsifiable feasibility analysis for a rectangular candidate in which N-segment bridges connect C3(i,j) to C9(i+1,j), while N+2-segment bridges connect C12(i,j) to C6(i,j+1). Green's-function reduction gives distinct directional couplings. Within a scalar nearest-neighbor model, this implies nonzero Bloch dispersion in both in-plane directions. Electronic connectivity is combined with independent requirements for useful absorption, robustly favorable charge-separation and hydrogen-reduction free energies, carrier survival, diffusion to an accessible platinum site, and interfacial electron injection. These quantities yield an explicit lower bound on the mass-normalized hydrogen-evolution rate. Feasibility is defined by the experimentally testable inequality as an independently determined, background-corrected limit of quantification; performance equal to the DBC benchmark is not required. An optional metal-conditioned extension describes how Mg or redox-active transition-metal states may modify energetic alignment while imposing an additional excited-state quenching constraint. The analysis supports prospective testing of the hydrogen-evolution half-reaction relevant to artificial photosynthesis, but does not establish catalyst-free hydrogen production, water oxidation, or overall water splitting.