从“格氏”的魔棒到“乐高”之城：金属与有机物的百年“牵手”传奇

doi:10.12461/PKU.DXHX202605063

摘要/Abstract

摘要： 2025年诺贝尔化学奖授予金属有机框架(MOFs)研究先驱，为公众重新认识这一类“分子建筑”材料提供了契机。本文以该奖项为切入点，回顾金属与有机组分连接方式在过去百余年中的演变：从格氏试剂所代表的金属-碳σ键，到维生素B₁₂所呈现的复杂钴配位结构和二茂铁所揭示的金属-π成键模式，再到齐格勒-纳塔催化剂对聚烯烃工业的深刻影响，最终过渡到以配位自组装和网状化学为核心的MOFs体系。文章旨在说明，MOFs并非孤立出现的新概念，而是金属有机化学、配位化学与材料化学长期积累后形成的重要成果；同时结合三位诺奖得主的代表性贡献，并介绍我国学者在乙烷选择性吸附、超薄MOF电催化剂和手性MOF催化等方面的代表性成果，展现基础研究如何逐步走向能源、环境和健康等应用前沿。

关键词: MOFs, 诺贝尔奖, 金属有机化学, 配位化学, 网状化学

Abstract: The 2025 Nobel Prize in Chemistry, awarded for the development of metal-organic frameworks (MOFs), provides a timely opportunity to revisit how chemists have connected metals with organic components over more than a century. Written for a general chemistry readership, this article follows several representative stages in that history. It begins with Grignard reagents and the polarity reversal of carbon in metal-carbon σ bonds, then turns to the complex cobalt coordination structure of vitamin B12 and the delocalized metal-π bonding revealed by ferrocene. The discussion next considers how Ziegler-Natta catalysts enabled the large-scale production of stereoregular polyolefins. It then turns to MOFs, in which metal nodes and organic linkers are assembled into extended networks through coordination bonds. The complementary contributions of Richard Robson, Susumu Kitagawa, and Omar M. Yaghi are described in terms of network design, functional gas adsorption, and reticular chemistry. Recent Chinese contributions to ethane-selective adsorption, ultrathin MOF electrocatalysts, and chiral MOF catalysis are also highlighted. By linking bonding concepts, historical experiments, and modern applications, the article emphasizes that MOFs did not emerge as an isolated invention, but from the long-term interaction of organometallic chemistry, coordination chemistry, and materials science. It also illustrates how fundamental research can gradually provide molecular tools for challenges in energy, environment, separation, and health.

Key words: MOFs, Nobel Prize, Organometallic chemistry, Coordination chemistry, Reticular chemistry

谢雨林, 陈思骄, 夏悦, 徐广, 储瑞. 从“格氏”的魔棒到“乐高”之城：金属与有机物的百年“牵手”传奇[J]. 大学化学, 2026, (): 2605063.

Yulin Xie, Sijiao Chen, Yue Xia, Guang Xu, Rui Chu. From Grignard’s magic wand to a molecular LEGO city: a centurylong saga of metal-organic connections[J]. University Chemistry, 2026, (): 2605063.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202605063

https://www.dxhx.pku.edu.cn/CN/Y2026/V/I/2605063

参考文献

[1] The Nobel Prize in Chemistry 2025: Press Release. [2026-07-20]. https://www.nobelprize.org/prizes/chemistry/2025/press-release/
[2] F. Fathieh, M.J. Kalmutzki, E.A. Kapustin, P.J. Waller, J. Yang, O.M. Yaghi, Sci. Adv. 2018, 4(6), eaat3198.
[3] A.M. Fracaroli, H. Furukawa, M. Suzuki, M. Dodd, S. Okajima, F. Gándara, J.A. Reimer, O.M. Yaghi, J. Am. Chem. Soc. 2014, 136(25), 8863.
[4] P. Horcajada, R. Gref, T. Baati, P.K. Allan, G. Maurin, P. Couvreur, G. Férey, R.E. Morris, C. Serre, Chem. Rev. 2012, 112(2), 1232.
[5] W.C. Zeise, Ann. Phys. Chem. 1831, 97(4), 497.
[6] E. Frankland, Q. J. Chem. Soc. 1850, 2, 297.
[7] V. Grignard, C. R. Hebd. Séances Acad. Sci. 1900, 130, 1322.
[8] The Nobel Prize in Chemistry 1912: Summary. [2026-07-20]. https://www.nobelprize.org/prizes/chemistry/1912/summary/
[9] G. Wilkinson, M. Rosenblum, M.C. Whiting, R.B. Woodward, J. Am. Chem. Soc. 1952, 74(8), 2125.
[10] E.O. Fischer, W. Pfab, Z. Naturforsch. B 1952, 7(7), 377.
[11] K. Ziegler, E. Holzkamp, H. Breil, H. Martin, Angew. Chem. 1955, 67(19–20), 541.
[12] G. Natta, P. Pino, P. Corradini, F. Danusso, E. Mantica, G. Mazzanti, G. Moraglio, J. Am. Chem. Soc. 1955, 77(6), 1708.
[13] H. Li, M. Eddaoudi, M. O’Keeffe, O.M. Yaghi, Nature 1999, 402(6759), 276.
[14] 邢其毅, 裴伟伟, 徐瑞秋, 裴坚, 基础有机化学: 上册. 第4版. 北京: 北京大学出版社, 2016: 440–442.
[15] D.C. Hodgkin, J. Kamper, J. Lindsey, M. Mackay, J. Pickworth, J.H. Robertson, C.B. Shoemaker, J.G. White, R.J. Prosen, K.N. Trueblood, Proc. R. Soc. Lond. A 1957, 242(1229), 228.
[16] The Nobel Prize in Chemistry 1964: Summary. [2026-07-20]. https://www.nobelprize.org/prizes/chemistry/1964/summary/
[17] R.B. Woodward, Pure Appl. Chem. 1973, 33(1), 145.
[18] T.J. Kealy, P.L. Pauson, Nature 1951, 168, 1039.
[19] S.A. Miller, J.A. Tebboth, J.F. Tremaine, J. Chem. Soc. 1952, 632.
[20] The Nobel Prize in Chemistry 1973: Summary. [2026-07-20]. https://www.nobelprize.org/prizes/chemistry/1973/summary/
[21] J. Chatt, L.A. Duncanson, J. Chem. Soc. 1953, 2939.
[22] The Nobel Prize in Chemistry 1963: Summary. [2026-07-20]. https://www.nobelprize.org/prizes/chemistry/1963/summary/
[23] B.F. Hoskins, R. Robson, J. Am. Chem. Soc. 1990, 112(4), 1546.
[24] Y. Kinoshita, I. Matsubara, T. Higuchi, Y. Saito, Bull. Chem. Soc. Jpn. 1959, 32(11), 1221.
[25] M. Kondo, T. Yoshitomi, H. Matsuzaka, S. Kitagawa, K. Seki, Angew. Chem. Int. Ed. Engl. 1997, 36(16), 1725.
[26] S. Horike, S. Shimomura, S. Kitagawa, Nat. Chem. 2009, 1(9), 695.
[27] N.W. Ockwig, O. Delgado-Friedrichs, M. O’Keeffe, O.M. Yaghi, Acc. Chem. Res. 2005, 38(3), 176.
[28] P.-Q. Liao, W.-X. Zhang, J.-P. Zhang, X.-M. Chen, Nat. Commun. 2015, 6, 8697.
[29] S. Zhao, Y. Wang, J. Dong, C.-T. He, H. Yin, P. An, K. Zhao, X. Zhang, C. Gao, L. Zhang, et al., Nat. Energy 2016, 1, 16184.
[30] X. Chen, H. Jiang, B. Hou, W. Gong, Y. Liu, Y. Cui, J. Am. Chem. Soc. 2017, 139(38), 13476.