{[Zn2(tcppda)(DPTzTz)2]·3DMF} (1)
{[Zn2（tcppda）（DPTzTz）2]·3DMF}(1),
Complex 1 was synthesized at 120 °C using Zn(NO3)3·6H2O and H4TCPPDA in DMF with the addition of HNO3 (see Supporting Information for synthetic details), and its structure was analyzed by single-crystal X-ray diffraction studies.
在 120 °C 下，使用 Zn（NO3）3·6H2O 和 H4TCPPDA在 DMF 中合成复合物 1，并添加 HNO3（合成细节见支持信息），其结构 w 通过单晶 X 射线衍射研究分析。
Complex 1 crystallizes in triclinic crystal system with a space group of P-1 (Table S1)
复合物 1 在空间群为 P-1 的三斜晶系中结晶（表 S1）.
The asymmetric unit contains two individual Zn(II) centers, one fully deprotonated tcppda 4- ligand, two linear DPTzTz ligand, and three DMF molecules (Fig. 1a)
不对称单元包含两个单独的 Zn（II） 中心、一个完全去质子化的 tcppda4 配体、两个线性 DPTzTz 配体和三个DMF 分子s（图 1a）.
Fig. 1a Coordination environment of Cd(II) center in 1, Symmetry code: #1 -1+x, y, z; #2 x, 1+y, z; #3 -1+x, 1+y, z; #4 x, y, -1+z.
图 1a中 Cd（II） 中心的配位环境 1，对称码： #1 -1+x， y， z; #2 x， 1+y， z; #3 -1+x， 1+y， z; #4 x、y、-1+z。
All the Zn(II) centers were coordinated by four oxygen atoms from three different tcppda4-ligands and two nitrogen atoms from two DPTzTz ligands, resulting a distorted octahedron coordination geometry. The bond lengths of Zn-O/N were located in the normal range of 2.001 Å- 2.305 Å. Among them, the bond lengths of Zn1-O4 and Zn2-O6 are slightly longer (2.241 Å and 2.305 Å), indicating that the forces between them are weaker
所有 Zn（II） 中心由来自三个不同 tcppda4 配体的四个氧原子和来自两个 DPTzTz 配体的两个氮原子配位，导致扭曲的八面体配位几何Zn-O/N 的键长位于 2.001 Å- 2.305 Å 的正常范围内。其中，Zn1-O4 和 Zn2-O6 的键长略长（2.241 Å 和 2.305 Å），表明它们之间的力较弱.
Selected bond distances and angles are listed in Table S1.
选定的键距离和角度列于表 S1 中。
CCDC number for complex 1 is xxxxxxx, and the data can be obtained free of charge from the Cam-bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
co mplex 1 的 CCDC 编号为xxxxxxx，数据可通过 www.ccdc.cam.ac.uk/data_request/cif 从 Cam-bridge 晶体学数据中心免费获取。
The tcppda4- ligand with C2h symmetry displays two coordination modes of bis-monodentate (μ2-η1: η1) and chelating (μ1-η1: η1)
具有 C2h 对称性的 tcppda 4 - 配体表现出双单齿 （μ2-η1η1） 和螯合 （μ1-η1η1） 的两种配位模式.
The two unequally sp3 hybridized N atoms result in all benzene rings of the tcppda4- ligand being noncoplanar. As shown in Fig. 2, taking the plane where the four carboxylic acid carbon atoms are located as a reference, the angles of the remaining four benzene rings as well as the central benzene ring to it are 27.13°, 42.01°, 40.30°，and 31.32°, respectively.
两个不相等的 sp3 杂化 N 原子导致 tcppda4- 配体的所有苯环都是非共面的。如图2 所示，以四个羧酸碳原子所在的平面为参考，其余四个苯环以及中心苯环与其的角度分别为 27.13°、42.01°、40.30° 和 31.32°。
Fig. 2 The coordinate modes and geometry of the tcppda4- ligand. (depicted by the angle between the benzoate plane and the plane formed by connecting the four carboxylate carbon atoms)
图 2 tcppda4- 配体的坐标模式和 geometry。 （由苯甲酸盐平面与连接四个羧酸盐碳原子形成的平面之间的夹角表示）
Zn1 and Zn2 were connected by two bidentate carboxylates of two H4tcppda ligands, constituting [Zn2(COO)2] secondary building unit (SBU) with the Zn1··· Zn2 distance of 4.116Å
Zn1 和 Zn2 通过两个 H4tcppda 配体的两个双齿羧酸盐连接，与 Zn1·· 构成 [Zn2（COO）2] 二级建筑单元 （SBU）Zn2 距离 4.116Å.
The [Zn2(COO)2] SBUs were bridged by the tcppda4- ions to form 2D neutral layer (Fig. S2). The adjacent layers were further connected by DPTzTz pillars to form a typical pillar-layered porous framework (Fig. S3)
[Zn2（COO）2] SBU 被 tcppda4- 离子桥接形成 2D 中性层（图 S2）相邻层进一步通过 DPTzTz 柱连接，形成典型的柱状层状多孔框架（图 S3）.
The two [Zn2(COO)2] SBUs in adjacent layers connect two linear DPTzTz ligands by Zn(II) centers, resulting in a cofacially arrange DPTzTz pairs. The cofacial stacking of one DPPTzTz ligand is offset relative to the other DPPTzTz (Fig. S4)
相邻层中的两个 [Zn2（COO）2] SBU 通过 Zn（II） 中心连接两个线性 DPTzTz 配体，形成表面排列的 DPTzTz 对。 一个 DPPTzTz 配体的共面堆叠相对于另一个 DPPTzTz 偏移（图 D）。 S4） .
An obvious π…π stacking distance between cofacial pairs of DPPTzTz is 3.893 Å, which means that electron transfer can take place within the framework of 1
一个明显的π......π DPPTzTz 的共面对之间的堆叠距离为 3.893 Å，这意味着电子转移可以在 1.
the cofacial dimer pairs of the DPPTzTz ligand in 1
DPPTzTz 配体的共面二聚体对 1
In 1, there are two types of 1D open channels, that is the smaller one with the pore dimension of 4.93 Å × 14.84 Å, and larger one with the pore dimension of 17.23 Å ×14.84 Å (Fig. 3).
在 1 中，有两种类型的 1D 开放通道，that 是孔径 为 4.93 Å × 14.84 Å 的较小通道，而较大的通道孔径为 17.23 Å ×14.84 Å（图 D）。 3）.
The inner walls of channels were densely by TPA and TzTz groups, all of which make activated 1a an excellent candidate for the iodine capture and catalytic CO2 cycloaddition reaction
通道内壁由 TPA 和 TzTz 基团密集，所有这些都使活化的 1a 成为碘捕获和催化 CO2 环加成反应的极好候选者.
The 3D framework of 1.
1.
Fig.3 View of two-fold interpenetrated 3D framework of 1
图 3 1 的两重穿插 3D 框架视图
拓扑分析：
Topologically, the [Zn2(COO)2] SBUs and TCPPDA4- ions can be regarded as 6-connected and 4-connected nodes, respectively, while DPTTZ acting as the linkers, thus the framework can be simplified as typically 4,6-connected pcu network (Fig. S4). Due to the high porosity, one pillar-layered framework was interpenetrated to another, to give overall a 2-fold interpenetrated architecture (Fig. 4b)
在拓扑学上，[Zn2（COO）2] SBU 和 TCPPDA4- 离子可以分别被视为 6 连接和 4 连接的节点，而 DPTTZ 充当连接节点，因此该框架可以简化为典型的 4,6 连接 pcu 网络（图 S4）由于高孔隙率，一个柱层框架与另一个柱层框架相互穿插，从而形成整体 2 倍互穿结构（图 4b）.
In spite of 2-fold interpenetration, complex 1 contains 35% (after removal of guest DMF molecules) accessible pore volume as calculated by using PLATON/SOLV.
尽管有 2 倍的互穿作用，但复合物 1 含有 35%（去除客体 DMF 分子后）的可及孔体积，使用 PLATON/SOLV 计算。
Fig. 4 Topology network of 1
图 4 1 的拓扑网络.
After activation (referred to as 1a), the framework remains intact (Figure S5), making 1a a potential ideal platform for applications such as adsorption/separation, catalysis, and fluorescence recognition.
活化后（称为 1a），框架保持完整（图S5），使 1a 成为吸附/分离、催化和荧光识别等应用的潜在理想平台。
The N2 adsorption isotherm of complex 1a show a typical type I feature (Figure S6), which gave a remarkable N2 adsorption quantity of 144.1 cm3g−1. The BET (Brunauer−Emmett−Teller) surface area of 1a was estimated to be 1022 m2g−1.
复合物 1a 的 N2 吸附等温线 显示出典型的I 型 al 特征（图 S6），其 N2 吸附量为 144。1 厘米3克-1。BET（Brunauer-Emmett-Teller） 的表面积估计为 be 1022 m2 g-1。
To evaluate the chemical and thermal stability of complex 1, the as-synthesized sample was treated under various conditions.
为了评价复合物 1 的化学和热稳定性，在各种条件下处理了合成的样品。
complex 1 maintained its overall structural integrity upon solvent removal and subsequent N2 adsorption (Figure S7)
复合物 1 在溶剂去除和随后的 N2 吸附后保持其整体结构完整性（图 S7）.
Stability tests were further performed on complex 1 immersed in water or different organic solvents for two weeks.
对浸入水或不同有机溶剂中的复合物 1 进一步进行稳定性测试两周。