Page 73 - 《精细化工》2022年第7期

第 7 期 于立冬，等: 金属-有机笼状化合物在限域催化领域的研究进展 ·1359·

图 17 Zn-ZPA 包合人工催化和天然酶的催化过程 [42]
Fig. 17 Catalytic process of synergism of artificial catalysis and natural enzyme in Zn-ZPA [42]

应机理有着重要的作用。通过主-客体间良好的超分 ligand design. X-ray, DFT and solution studies of the effect of
N-methylation and N-benzylation of 1, 4, 10, 13-tetraoxa-7, 16-
子作用，限域催化拉近了底物与金属离子的接触距 diazacyclooctadecane on its affinity for selected transition and post-
离、提高了局部浓度，使得 MOCs 比传统非限域催 transition metal ions[J]. Journal of the Chemical Society Dalton
Transactions, 2001, (5): 614-620.
化剂效率更高、选择性更好。近年来，中国在 MOCs [5] SZEJTLI J. Cyclodextrin technology[M]. Boston: Kluwer Academic,
机理研究中取得了巨大进步，中国科研人员利用 1988: 1-185.
[6] SIEGEL B, BRESLOW R. Lyophobic binding of substrates by
2+
3+
2+
Co 、Ru 、Ce 等金属离子的氧化还原活性构建了 cyclodextrins in nonaqueous solvents[J]. Journal of the American
限域体系下的光致产氢、产氧体系以及二氧化碳还 Chemical Society, 1975, 97(23): 6869-6870.
[7] LEE J W, SAMAL S, SELVAPALAM N, et al. Cucurbituril homologues
原体系，大大提高了产氢、产氧和二氧化碳还原效 and derivatives: New opportunities in supramolecular chemistry[J].
2+
2+
率；在 Pd 等高活性催化金属基础上，发展了 Ni 、 Accounts of Chemical Research, 2003, 36: 621-630.
[8] KIM H, KIM Y, YOON M, et al. Highly selective carbon dioxide
2+
Zn 等过渡金属作为配位中心催化，用于 Michael sorption in an organic molecular porous material[J]. Journal of the
加成、Diels-Alder 反应、Knoevenagel 反应以及光二 American Chemical Society, 2010, 132(35): 12200-12202.
[9] YANG L, ZHANG D, YAN H, et al. Flexible-ligand-based self-adaptive
聚反应等，拉近了催化中心与底物距离，从而提高 metal-organic material for supramolecular selective recognition of
了底物在 MOCs 中的局部浓度。另外，配体的可修 smilar natural molecules[J]. Inorganic Chemistry, 2019, 58: 4067-
4070.
饰性为限域催化增添了无限生机，为不对称催化领 [10] FUJITA M, OGURO D, MIYAZAWA M, et al. Self-assembly of ten
域作出了贡献。 molecules into nanometre-sized organic host frameworks[J]. Nature,
1995, 378: 469-471.
MOCs 在超分子领域中具有极大应用潜力。 [11] AUGUST D P, NICHOL G S, LUSBY P J. Maximizing coordination
MOCs 的空腔结构越来越多样，功能性质越来越多， capsule-guest polar interactions in apolar solvents reveals significant
binding[J]. Angewandte Chemie International Edition, 2016, 55(48):
MOCs 的发展极大地促进了超分子领域的发展。目 15022-15026.
前，中国在 MOCs 领域的研究仍停留在基础阶段， [12] PRAKASAM T, DEVARAJ A, SAHA R, et al. Metal-organic self-
Assembled trefoil knots for C-Br bond activation[J]. ACS Catalysis,
而 MOCs 的实际应用还需要进一步探索。构建更加
2019, 9(3): 1907-1914.
稳定性的 MOCs 材料，是其广泛应用的关键。中国 [13] ZHAO L, WEI J, LU J, et al. Renewable molecular flasks with
NADH models: Combination of light-driven proton reduction and
在医药和化工领域仍面临着巨大挑战，发展 MOCs
biomimetic hydrogenation of benzoxazinones[J]. Angewandte Chemie
对制造更高效、对映选择性更好的催化剂有着非凡 International Edition, 2017, 56(30): 8692-8696.
[14] LU C, ZHANG M, TANG D, et al. Fluorescent metallacage-core
意义，有利于中国在医药和化工领域的大力发展。
supramolecular polymer gel formed by orthogonal metal coordination
and host-guest interactions[J]. Journal of the American Chemical
参考文献： Society, 2018, 140(24): 7674-7680.
[1] SWIEGERS G F, MALEFETSE T J. New self-assembled structural [15] FUJITA M, UMEMOTO K, YOSHIZAWA M, et al. Molecular
motifs in coordination chemistry[J]. Chemical Reviews, 2000, 100(9): paneling via coordination[J]. Chemical Communications, 2001, 6:
3483-3537. 509-518.
[2] LEHN J. Supramolecular chemistry—Scope and perspectives [16] SEIDEL S R, STANG P J. High-symmetry coordination cages via
molecules, supermolecules, and molecular devices (Nobel Lecture)[J]. self-assembly[J]. Accounts of Chemical Research, 2002, 35: 972-983.
Angewandte Chemie International Edition, 1988, 27(1): 89-112. [17] CAULDER D L, RAYMOND K N. The rational design of high
[3] CRAM D J, CRAM J M. Design of complexes between synthetic symmetry coordination clusters[J]. Journal of the Chemical Society
hosts and organic guests[J]. Accounts of Chemical Research, 1978, Dalton Transactions, 1999, 8(8): 1185-1200.
11(1): 8-14.
[4] HAMBLEY T W, LINDOYL F, REIMERS J R, et al. Macrocyclic （下转第 1410 页）