Hernández-Pacheco Paulina, Zelada-Guillén Gustavo A, Escárcega-Bobadilla Martha V
Department of Organic Chemistry, School of Chemistry, National Autonomous University of Mexico (UNAM). Circuito Escolar s/n, Ciudad Universitaria, Mexico City 04510, Mexico.
ACS Omega. 2025 Aug 9;10(32):36382-36395. doi: 10.1021/acsomega.5c04731. eCollection 2025 Aug 19.
Edge oxidized graphene oxide (EOGO) is a promising graphene variant that has remained broadly unexplored as a two-dimensional (2D) supramolecular building block. This work aimed to construct graphene supramolecular frameworks (GSFs) using EOGO building blocks and [PdCl(3,5,7-triaza-7-phosphaadamantane)] (Pd-PTA) as ditopic guest linkers through noncovalent reticulation. Pd-PTA facilitated host-guest-host interconnection of the graphene units selectively through supramolecular hinges based on a Ni-Salphen scaffold hydroxylated at variable positions but formerly grafted to the carboxyl moieties exclusively present at the EOGO edges to maximize directional efficiency in reticulation. Synthesis and characterization of the supramolecular complexes formed between the Ni-Salphen variants and Pd-PTA, together with spectrophotometric titrations in solution, have confirmed concurrence of 1:1 and 2:1 stoichiometries for the [Ni-Salphen]/[Pd-PTA] systems. In contrast, EOGO--[Ni-Salphen] hybrid counterparts developed stoichiometry 1:1 for [Ni]/[Pd-PTA] at up to 1000-fold higher and depicted the emergence of successive host-guest-host concatenation at [Ni] via 1:2 species formed through similar strength ( ∼ ). This stoichiometric inversion apparently enabled a cooperative oligomerization, as was further suggested by Hill plots and a concentration-dependent rise in fluorescence that progressed asymptotically upon the addition of Pd-PTA. Kinetically controlled assembly and solvent evaporation facilitated long-range arrangements, which we confirmed qualitatively and quantitatively by solid-state evaluations, thus offering a next generation of supramolecular frameworks.
边缘氧化石墨烯（EOGO）是一种很有前景的石墨烯变体，作为二维（2D）超分子构建块，它在很大程度上仍未得到充分探索。这项工作旨在使用EOGO构建块和[PdCl(3,5,7-三氮杂-7-磷杂金刚烷)]（Pd-PTA）作为双位点客体连接体，通过非共价网状化构建石墨烯超分子框架（GSF）。Pd-PTA通过基于在可变位置羟基化但以前仅接枝到EOGO边缘特有的羧基部分的Ni-Salphen支架的超分子铰链，选择性地促进石墨烯单元的主客体-主客体互连，以最大化网状化中的定向效率。Ni-Salphen变体与Pd-PTA之间形成的超分子配合物的合成与表征，以及溶液中的分光光度滴定，已证实[Ni-Salphen]/[Pd-PTA]体系中1:1和2:1化学计量比的同时存在。相比之下，EOGO-[Ni-Salphen]杂化对应物在高达1000倍的浓度下，[Ni]/[Pd-PTA]的化学计量比为1:1，并通过类似强度（~）形成的1:2物种描绘了在[Ni]处连续的主客体-主客体串联的出现。这种化学计量反转显然实现了协同低聚，正如希尔图和添加Pd-PTA后荧光随浓度增加而渐近上升所进一步表明的那样。动力学控制的组装和溶剂蒸发促进了长程排列，我们通过固态评估对其进行了定性和定量确认，从而提供了新一代的超分子框架。
