Switching the Zinc Diphosphonates from 1D Chain to 2D Layer and 3D Framework by the Modulation of a Flexible Organic Amine

Abstract

A series of s mediated by a long and flexible amine 1,2-bis(3-aminopropylamino)ethane (BAPEN), were successfully assembled, showing diverse structures with different dimensions. Compound 1 displays an infinite Zn-HEDP chain that is decorated by chelating BAPEN. Compound 2 possesses an anionic Zn-HEDP layer structure with the protonated BAPEN as a charge balancer. Compound 3 features a 3D Zn-HEDP network with protonated BAPEN as the template. The structural diversity for 1−3 from 1D to 2D and 3D was modulated by BAPEN in the assembly process (coordination role for 1 and template role for 2 and 3) together with the different reaction conditions. The photoluminescence properties of compounds 1−3 are investigated. The results show that the solids 1−3 exhibit intense blue fluorescence at ambient temperature under UV light irradiation. Moreover, the proton conduction behavior for compound 3 has been studied.

Charge Separated One-Dimensional Hybrid Cobalt/Nickel Phosphonate Frameworks: A Facile Approach to Design Bifunctional Electrocatalyst for Oxygen Evolution and Hydrogen Evolution Reactions

“…Of late, the advancement of transition-metal-based materials such as oxides, nitrides, sulfides, selenides, hydroxides, phosphides, phosphates, and various composite materials are considered as excellent catalysts for boosting electrochemical water splitting performance by replacing precious platinum/iridium catalysts. − The selection of flexible phosphonate groups along with incorporation of variable templated organoamines in hybrid metal phosphonate structures not only lead to a variety of structures but also serve as charge separators with modulated catalytic activity. − Interestingly, the lower dimensional transition metal phosphonate are often exciting for their strange magnetic behaviors and field-induced transitions. − However, among plentiful stimulating properties of hybrid metal phosphonates, the electrocatalytic water splitting reaction remains less explored so far. − With our continuous effort with metal phosphonates, − herein we have isolated two new hybrid one-dimensional transition-metal phosphonate chain structures with templated TETA through a hydrothermal pathway (i.e., [H 2 TETA]­[M­(H 2 hedp) 2 ]·2H 2 O, where M = Co for I , Ni for II ; H 4 hedp = 1-hydroxyethane-1,1-diphosphonic acid; TETA = triethylenetetramine) for the investigation of their electrochemical behaviors toward OER and HER. The present study not only explores the potential of any low cost bifunctional OER/HER catalyst designed by organophosphonate ligands but also exposes a promising avenue to explore stable, efficient, and precious-metal-free lower-dimensional framework structures as electrocatalysts.…”

Precise Control of the Dimension of Homochiral Metal-Organic Frameworks （MOFs) and Their Luminescence Properties

“…然而, 设计和合成这些不同维度和拓扑结构的材料 仍旧代表了当前合成化学中最具挑战性的任务之一. 基 于配位化学的多维杂化材料的合理设计和自组装是解 决该问题的一种有效途径 [8][9][10] . 近年来, 该领域的研究 主要集中在通过强的金属配位键或弱作用(如氢键和 π-π 相互作用)自组装而成一维链或管、二维层和三维多孔 的 MOFs [11][12] .…”

“…截至目前, MOFs 的研究主要集中在多孔的三维结构, 作为一种新 型的孔材料, 在气体吸附和储存、催化、传感、光学、 磁性和药物传输等领域表现出良好的性能 [16] . 在过去 的二十多年中, 已报道的一维、二维和三维 MOFs 主要 由不同的有机配体和金属 [6,[17][18][19] 或不同的有机配体和相 同的金属 [20][21][22][23][24] 或不同的金属和相同的配体组成 [11,12,[25][26][27][28][29][30][31] , 而由相同的有机配体和金属离子合成的一维、二维和三 维 MOFs 是有限的 [10,[32][33][34][35] . 因为在合成 MOFs 时, 需要 考虑许多因素, 例如: 有机配体的柔性、配位点的数量 和方向、金属配位的可能性、金属离子和配体的物质的 量比、溶液的 pH 值、溶剂、温度、抗衡离子、辅助配 体等.…”

“…因此, 采用变换反应条件 来精准调控具有相同组分的多维 MOFs 的合成是一项更 有意义的研究. 迄今为止, 只有少数报道运用溶剂调 控 [32] 、pH 调控 [33] 、辅助配体作用 [10,36] 组装而成多维 MOFs. 为了提高调控方法的可设计性和多样性, 有必 要开发更高效、更精准的合成策略.…”

“…为了提高调控方法的可设计性和多样性, 有必 要开发更高效、更精准的合成策略. 而且, 目前由同一 有机配体和金属构建的一维、二维和三维 MOFs 主要是 非手性的 [10,[32][33][34][35] , 而多维同手性 MOFs 则极为罕见. 鉴 于手性 MOFs 在对映选择性传感 [37][38][39] 、分离 [40][41] 、催 化 [15] 等方面的广泛应用而变得越来越重要, 这促使我 们去开发其合理的合成方法及其应用研究.…”