Guanine nucleotide directed co-assembly with Pt-complexes for tailoring chiroptical properties and multimodal molecular recognition

TL;DR

This paper shows how different guanine nucleotides control the co-assembly of Pt-complexes, leading to unique optical properties and molecular recognition.

Contribution

The study reveals how phosphate number in guanine nucleotides modulates co-assembly and optical responses for molecular recognition.

Findings

GMP enables efficient ground-state chiral induction and enhanced circular dichroism (CD).

GDP increases photoluminescence (PL) efficiency through metallophilic interactions and restricted rotation.

GTP leads to enhanced circularly polarized luminescence (CPL) with asymmetric assembly.

Abstract

Modulating co-assembly behavior via a subtle structural difference in biomolecular partners holds great potential, yet remains underexplored. Herein, we report an in-depth photophysical investigation, revealing that guanine nucleotides (GMP, GDP, and GTP) direct the co-assembly of organoplatinum complex (A), where the phosphate number controls the ribose–Pt(ii) distance and yields distinct supramolecular structures with unique chiroptical properties. For the monophosphate guanine nucleotide (GMP), the close distance between the chiral unit and the Pt(ii) center enables efficient ground-state chiral induction and leads to enhanced circular dichroism (CD). While the diphosphate guanine nucleotide (GDP) adopts partially intercalated edge-associated geometry and enhanced photoluminescence (PL) efficiency by minimizing non-radiative transition through facilitating metallophilic interactions and restricting the rotational freedom. The triphosphate guanine nucleotide (GTP) gives rise to an asymmetrically organized assembly, and the chiral ribose units are completely located outside the molecular layer, which lead to enhanced circularly polarized luminescence (CPL). The multimodal optical outputs enable specific recognition of GMP, GDP, and GTP, respectively, offering a multifunctional strategy for molecular discrimination based on optical multi-channel responses. By bridging the molecular-scale electronic structure, spatial interaction sites, and supramolecular packing, this work highlights the underlying structure–function coupling that governs diverse optical outputs in these nucleotide-directed co-assemblies.

Supramolecular co-assembly driven by phosphate variation modulates spatial interaction and supramolecular packing, enabling mode-selective chiroptical responses and precise molecular recognition.

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