网状化学和等网状扩展

2002

Omar M. Yaghi
Michael O’Keeffe

（图片仅供参考）

网状化学是MOF的设计原理，涉及将预定的分子结构单元（金属节点和有机连接体）组装成具有可预测拓扑结构的有序扩展结构。该原理的一个关键示例是等网状MOF的合成，其中底层网络拓扑结构得以保持，同时通过使用逐渐加长的有机连接体系统地扩展孔径。

Reticular chemistry elevates the synthesis of materials from a trial-and-error process to a more deterministic, design-based science. It treats the metal clusters (Secondary Building Units, SBUs) and organic linkers as pre-defined geometric shapes (e.g., an octahedral SBU and a linear linker). By understanding the coordination preferences of the metal and the geometry of the linker, chemists can predict the resulting network topology before synthesis. The most famous example of this is the Isoreticular MOF (IRMOF) series, which is based on the archetypal MOF-5 structure. MOF-5 has a primitive cubic (pcu) topology formed from Zn4O octahedral SBUs and linear 1,4-benzenedicarboxylate (BDC) linkers.

The concept of isoreticular expansion was demonstrated by replacing the BDC linker with longer, but geometrically similar, dicarboxylate linkers like 2,6-naphthalenedicarboxylate (NDC) or 4,4′-biphenyldicarboxylate (BPDC). The resulting materials, IRMOF-8 and IRMOF-10 respectively, retained the same pcu network topology as MOF-5 but featured significantly larger pores. This systematic variation allowed for a direct correlation between linker length, pore size, and properties like gas uptake capacity, proving that MOF properties could be fine-tuned in a highly controlled manner. This principle has been extended to numerous other network topologies and building block combinations, solidifying MOFs as a prime example of programmable matter at the molecular level.

化学, Crystal Structure, 增材制造设计（DfAM）, 设计思维, 材料科学, 流程优化, 产品开发, 质量管理

UNESCO Nomenclature: 2203

– Inorganic chemistry

类型

Design Principle

中断

Foundational

用法

广泛使用

前体

超分子化学概念，作者：jean-marie lehn
格哈德·施密特 (Gerhard Schmidt) 提出的晶体工程原理
单晶X射线衍射在结构测定中的应用进展
早期配位聚合物的合成
晶体结构拓扑分析

应用程序

选择性分子筛孔径的系统调节
rational design of 催化剂 with controlled active site spacing
fundamental studies of gas adsorption in confined spaces
创建分层多孔结构
用于封装蛋白质等大分子的框架设计

专利：

潜在创新理念

可编程 MOF，可根据光或热改变孔径
multi-component mofs (MT-MOFs) with precisely arranged, different linkers for complex catalytic cascades
专为制药行业对映选择性分离而设计的手性 MOF
基于 MOF 的逻辑门，其中化学输入触发结构变化
根据第一原理设计的负热膨胀材料
按需捕获和释放分子的动态框架
mof ‘sponges’ for crystallizing and determining the structure of otherwise non-crystallizable molecules
具有精确设计缺陷的框架，可增强催化活性
互穿mof结构增强机械稳定性
将 MOF 与聚合物相结合以提高加工性能的复合材料

Related to: reticular chemistry, isoreticular, MOF, irMOF, crystal engineering, topology, secondary building unit, SBU, rational design, pore size tuning.

历史背景

Researcher manipulating carbon nanotubes with atomic force microscope in materials science lab.

碳纳米管

碳纳米管 (CNT) 是由单层碳原子（石墨烯）卷曲而成的圆柱形分子。它们可以是单壁 (SWCNT) 或多壁 (MWCNT)。它们拥有非凡的性质，包括优异的抗拉强度（约 100 GPa）、高电导率和高热导率。它们的电子行为（金属性或半导体性）取决于其手性，即石墨烯晶格卷曲的角度。

Precision balance scale and calibrated glassware in a laboratory for metrology applications.

ISO 5725 Definition of Accuracy

The ISO 5725 standard defines accuracy as the combination of trueness and precision. Trueness is the closeness of the mean of a large series of measurements to the accepted reference value, quantifying systematic error or bias. Precision is the closeness of agreement among a set of results, quantifying random error. Thus, accuracy requires both high trueness and high precision.

Superhydrophobic lotus leaf demonstrating self-cleaning properties in surface physics.

莲花效应：超疏水性和自清洁表面

The Lotus effect describes the self-cleaning property of the lotus plant's leaves. Its surface is covered in microscopic papillae coated with epicuticular wax crystals, creating a superhydrophobic surface. Water droplets bead up with a high contact angle ([latex]\theta > 150^{\circ}[/latex]) and low roll-off angle, picking up dirt particles as they roll off, thus cleaning the leaf.

网状化学和等网状扩展