3,8-bis(4-carboxyphenyl)phenanthroline

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 3,8-bis(4-carboxyphenyl)phenanthroline
• 英文别名: 4,4'-(1,10-Phenanthroline-3,8-diyl)dibenzoic acid；4-[8-(4-carboxyphenyl)-1,10-phenanthrolin-3-yl]benzoic acid
• 化学式: C₂₆H₁₆N₂O₄
• 分子量: 420.424
• InChiKey: RZPUEVQJLMTUFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  100
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,8-bis(4-carboxyphenyl)phenanthroline 、 水 、 氯化锆(IV) 在 三氟乙酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 生成
  参考文献：
  名称：

  Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations

  摘要：

  基于以氮为供体的有机桥联配体，包括基于1,3-二酮亚胺（NacNac）、联吡啶和柳酸亚胺的金属-有机框架（MOFs）组成物被合成，然后用金属前驱体如第一行过渡金属的络合物进行后合成金属化。有机桥联配体的金属络合物也可以直接并入MOFs中。MOFs提供了一个多功能的、可回收和可重复使用的单点固体催化剂家族，用于催化各种不对称有机转化。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。

  公开号：

  US10647733B2
• 作为产物：
  描述：

  3,8-二溴菲罗啉 在 四(三苯基膦)钯 、 cesium fluoride 、 sodium hydroxide 作用下， 以 乙二醇二甲醚 、 乙醇 为溶剂， 反应 111.0h， 生成 3,8-bis(4-carboxyphenyl)phenanthroline
  参考文献：
  名称：

  金属有机骨架整合铜光敏剂和 SBU 负载的铁催化剂用于光催化产氢

  摘要：

  我们在此报告了一系列金属有机框架 (MOFs) FeX@Zr6-Cu 的合成，包括亚铜光敏连接剂 (Cu-PSs) 和催化活性的 FeII 中心，支撑在二级构建单元 (SBU) 上用于光催化 H2进化。Cu-PS 和 SBU 支持的 Fe 位点之间的接近 (~1 nm) 以及通过周期性有序的 SBU 稳定 Fe 位点导致 FeX@Zr6-Cu 的光催化析氢活性非常高，周转数和周转频率高达 33,700高达 880 h-1。FeX@Zr6-Cu 的光催化析氢活性与 X 抗衡阴离子的不稳定性相关，表明不稳定的 X 基团产生的 Fe 位点的开放配位环境促进了析氢前 Fe 氢化物中间体的形成。

  DOI：

  10.1021/jacs.0c03906

文献信息

• Metal–Organic Frameworks Integrate Cu Photosensitizers and Secondary Building Unit-Supported Fe Catalysts for Photocatalytic Hydrogen Evolution
  作者：Yunhong Pi、Xuanyu Feng、Yang Song、Ziwan Xu、Zhong Li、Wenbin Lin

  DOI：10.1021/jacs.0c03906

  日期：2020.6.10

  SBU-supported Fe sites and stabilization of Fe sites by periodically ordered SBUs led to exceptionally high photocatalytic H2 evolution activity for FeX@Zr6-Cu with turnover numbers of up to 33,700 and turnover frequencies of up to 880 h-1. Photocatalytic H2 evolution activities of FeX@Zr6-Cu correlate with the lability of X counter anions, suggesting open coordination environments of Fe sites generated by

  我们在此报告了一系列金属有机框架 (MOFs) FeX@Zr6-Cu 的合成，包括亚铜光敏连接剂 (Cu-PSs) 和催化活性的 FeII 中心，支撑在二级构建单元 (SBU) 上用于光催化 H2进化。Cu-PS 和 SBU 支持的 Fe 位点之间的接近 (~1 nm) 以及通过周期性有序的 SBU 稳定 Fe 位点导致 FeX@Zr6-Cu 的光催化析氢活性非常高，周转数和周转频率高达 33,700高达 880 h-1。FeX@Zr6-Cu 的光催化析氢活性与 X 抗衡阴离子的不稳定性相关，表明不稳定的 X 基团产生的 Fe 位点的开放配位环境促进了析氢前 Fe 氢化物中间体的形成。
• Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation
  作者：Kuntal Manna、Teng Zhang、Francis X. Greene、Wenbin Lin

  DOI：10.1021/ja512478y

  日期：2015.2.25

  We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H borylation of arenes using B2pin2. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C-H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.
• METAL-ORGANIC FRAMEWORKS CONTAINING NITROGEN-DONOR LIGANDS FOR EFFICIENT CATALYTIC ORGANIC TRANSFORMATIONS
  申请人：The University of Chicago

  公开号：US20170182486A1

  公开（公告）日：2017-06-29

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
• Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
  申请人：The University of Chicago

  公开号：US10647733B2

  公开（公告）日：2020-05-12

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

  基于以氮为供体的有机桥联配体，包括基于1,3-二酮亚胺（NacNac）、联吡啶和柳酸亚胺的金属-有机框架（MOFs）组成物被合成，然后用金属前驱体如第一行过渡金属的络合物进行后合成金属化。有机桥联配体的金属络合物也可以直接并入MOFs中。MOFs提供了一个多功能的、可回收和可重复使用的单点固体催化剂家族，用于催化各种不对称有机转化。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。
• Metal–Organic Frameworks Significantly Enhance Photocatalytic Hydrogen Evolution and CO₂ Reduction with Earth-Abundant Copper Photosensitizers
  作者：Xuanyu Feng、Yunhong Pi、Yang Song、Carter Brzezinski、Ziwan Xu、Zhong Li、Wenbin Lin

  DOI：10.1021/jacs.9b12229

  日期：2020.1.15

  We report here the design of two multifunctional metal-organic frameworks, mPT-Cu/Co and mPT-Cu/Re, comprising of cuprous photosensitizers (Cu-PSs) and molecular Co or Re catalysts for photocatalytic hydrogen evolution (HER) and CO2 reduction (CO2RR), respectively. Hierarchical organization of Cu-PSs and Co/Re catalysts in these MOFs facilitates multielectron transfer to drive HER and CO2RR under visible

  我们在此报告了两种多功能金属有机骨架 mPT-Cu/Co 和 mPT-Cu/Re 的设计，包括用于光催化析氢 (HER) 和 CO2 还原的亚铜光敏剂 (Cu-PSs) 和分子 Co 或 Re 催化剂(CO2RR)，分别。这些 MOF 中 Cu-PSs 和 Co/Re 催化剂的分级组织促进了多电子转移以驱动可见光下的 HER 和 CO2RR，mPT-Cu/Co 的 HER 转换数 (TON) 为 18700，mPT-的​​ CO2RR TON 为 1328 Cu/Re，比其均质对照提高了 95 倍。