Self‐Assembly of Molecular Borromean Rings from Bimetallic Coordination Rectangles

Huang, Shengbing; Lin, Yue‐Jian; Li, Zhenhua; Jin, Guo‐Xin

doi:10.1002/anie.201406193

Cited by 128 publications

(51 citation statements)

References 36 publications

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“…Currently, a series of discrete two-dimensional (2D) macrocycles, three-dimensional (3D) cages, and nanomaterials with well-defined sizes and shapes were constructed by coordination-driven self-assembly. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] In this field, Stang and co-workers 51 reported the first TPE-based supramolecular cage, which brought about the recent flourishing of AIE-active metalla-supramolecular cages with tunable properties. [52][53][54] Among most of these structures, the TPE moieties were either attached or embedded in the supramolecules, and their emissions still followed the classic AIE principle.…”

Section: Introductionmentioning

confidence: 99%

Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands

Jiang

Zhang

et al. 2020

CCS Chem

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We report the preparation and emission properties of tetraphenylethylene (TPE)-based metallacages with aggregation-induced emission (AIE) activities through coordination-driven self-assembly. Two supramolecular cages, [Zn 6 LA 3 ] and [Zn 6 LB 3 ], were assembled via TPE-decorated terpyridine (tpy) ligands, LA and LB, respectively, with Zn(II) ions. We performed a subtle change by introducing extra alkyne connectivity into LB to increase the degree of conjugation and geometric constraint, compared with LA. As a result, we obtained a highly emissive cage, [Zn 6 LB 3 ], even in a dilute solution. At a low temperature, the intramolecular rotation of TPE was further restricted, thus, resulting in a significant increase in fluorescence. Through mixing LA and LB, we obtained a series of hybrid cages, which also indicated that the emission was enhanced with highly abundant LB in the cages. Further, we studied the emission behaviors of the ligands and cages in solid state under external pressure. Upon gradual increase of the external pressure, the luminescence of [Zn 6 LB 3 ] increased initially, due to further rotation restriction, which was followed by quenching under 6.32 Gpa, owing to the tight packing of the supramolecules. The subsequent release of the pressure resulted in cage recovery of the emission.

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Section: Introductionmentioning

confidence: 99%

Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands

Jiang

Zhang

et al. 2020

CCS Chem

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“…Hence, au niversal methodology to developafamily of heterometallic coordination structures with variable sizes and actives ites is yet to be reported. [6] Recently,w er eported as eries of size-extending heterometallic metallorectangles, [7] using the heteroligand synthetic strategy based on Cp*Rh metal corners. [8] However,B orromean-type ring structures that block the inner cavities were found when long bridging ligands wereused.…”

Section: Introductionmentioning

confidence: 99%

Discrete Rectangles, Prisms, and Heterometallic Cages from a Conjugated Cp*Rh‐Based Building Block

Zhang

Lin

et al. 2015

Chemistry A European J

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By carefully selecting an existing synthetic strategy and suitable coordination subunits, constructing desired coordination geometries is no longer that difficult to accomplish. Herein, a new strategy to construct a series of unprecedented structures by using conjugated Cp*Rh-based complex BN-OTf (Cp* = η(5)-C5Me5) as the building block is proposed. DFT calculations revealed extensive delocalized π bonds in the subunit. With BN-OTf, rectangular macrocycles TN-bpy and TN-bpe were controllably synthesized. Single-crystal XRD studies confirmed one-dimensional stacking channels for the tetranuclear structure. Notably, the starting ligand imidazole-4,5-dicarboxylate was found to act not only as a tetradentate but also as a hexadentate ligand that can coordinate to further metal ions. Subsequently, [4 Rh+1 M] heterometallic complexes HMZ (M = Cu and Zn) were accessed by chelating borderline hard/soft Lewis acids. With TN-Linker or HMZ, two routes resulted in the [8 Rh+2 M] heterometallic cages HMC (M = Cu and Zn) with excellent crystallinity and stability. Surprisingly, when BN-OTf bonded to rhodium itself, triangular prisms TP-Linker were obtained with high solubility after being linked by bipyridine linkers. Both the X-ray structure and (1)H NMR spectrum confirmed the novel isomerization of the triangular structures. All of the compounds were obtained in high yields and were fully characterized by (1)H NMR spectroscopy, elemental analysis, IR spectroscopy, and in most cases single-crystal X-ray structure determination.

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“…[33,34] However, htpy À Ru II À tpyi connections are seldom used to assemble large and complex supramolecular architectures because of the absence of selectivity and reversibility.W eh erein report the construction of different generations (G1-G3) of Sierpiń ski triangles by combining Ru II and Zn II or Cd II in astepwise approach. [28,30,[35][36][37][38][39] In the first step,metallo-organic ligands with htpy À Ru II À tpyi connectivity were designed and synthesized as building blocks with enhanced selectivity and specificity.I nt he second step,t hese building blocks were assembled with Zn II or Cd II through highly reversible coordination to form large architectures in am olecular puzzling approach (Figure 1a nd Scheme 1). This approach is reminiscent of the specificity of an enzyme that is based on the structural and conformational complementarity between enzyme and substrate.In our initial study,Z n II was used to replace Cd II in the self-assembly of V and K with aprecise stoichiometric ratio of V/K/Zn = 3:3:9a ccording to ap revious study.…”

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Constructing High‐Generation Sierpiński Triangles by Molecular Puzzling

Wang

Jiang

et al. 2017

Angewandte Chemie

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Three generations of metalated trigonal supramolecular architectures,s o-called metallo-triangles,w ere assembled from terpyridine (tpy) complexes.T he first generation (G1) metallo-triangles were directly obtained by reacting ab is(terpyridinyl) ligand with a608 8 bite angle and Zn II ions.The direct self-assembly of G2 and G3 triangles by mixing organic ligands and Zn II ,however,only generated amixture of G1 and G2, as well as at race amount of insoluble polymer-like precipitate.T herefore,amodular strategy based on the connectivity of htpyÀRu 2+ Àtpyi was employed to construct two metallo-organic ligands for the assembly of G2 and G3 Sierpiń ski triangles.T he metallo-organic ligands L A and L B with multiple free terpyridines were obtained through Suzuki cross-coupling of the Ru II complexes,and then assembled with Zn II or Cd II to obtain high-generation metallo-triangular architectures in nearly quantitative yield. The G1-G3 architectures were characterized by NOESY and DOSY NMR spectroscopy, ESI-MS,T WIM-MS,a nd transmission electron microscopy.Asone of the most well-known and versatile fractal geometries,t he Sierpiń ski triangle was first formulated by the Polish mathematician Waclaw Sierpiń ski. [1] TheS ierpiń ski triangle has attracted increasing attention in science,t echnology,e ngineering,m ath, and art. In particular, recent developments in supramolecular chemistry [2][3][4] and/or selfassembly [5,6] have allowed chemists and physicists to explore this fractal geometry at am olecular level. Along with theoretical predictions, [7] different generations of Sierpiń ski triangles have been obtained by making use of halogen bonding, [8] hydrogen bonding, [9] and coordination [10][11][12] in ultrahigh vacuum by surface self-assembly.H owever,c onstructing discrete generations of Sierpiń ski triangles instead of mixtures still remains achallenge in surface self-assembly.Coordination-driven supramolecular chemistry [13][14][15][16][17][18][19][20][21][22][23][24][25][26] in solution may provide an alternative approach to obtain different generations of Sierpiń ski triangles in ap recisely controlled manner. Newkome and co-workers reported the terpyridine (tpy) based molecular Sierpiń ski metallo-triangle G2, which was assembled based on a608 8-oriented bis(terpyridine) V with a6 0 8 8 bite angle,1 ,2,3,4-tetra(terpyridine) K, and Cd II . [27] In the synthesis of higher-generation Sierpiń ski triangles,however, the undesired formation of low-generation triangles or coordination polymers by self-sorting of individual ligands cannot be avoided through simple stoichiometry control in the multicomponent self-assembly.It is well-known that in tpy-based supramolecular chemistry,R u II and Fe II coordinate more strongly to tpy than Cd II and Zn II . [28][29][30][31][32] Moreover, htpy À Ru 2+ À tpyi connectivities are remarkably stable and tolerate harsh chemical processes,f or example,h igh temperatures,b asic conditions,a nd column chromatography.R u II -tpy complexes have been extensively studied for use in d...

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Self‐Assembly of Molecular Borromean Rings from Bimetallic Coordination Rectangles

Cited by 128 publications

References 36 publications

Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands

Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands

Discrete Rectangles, Prisms, and Heterometallic Cages from a Conjugated Cp*Rh‐Based Building Block

Constructing High‐Generation Sierpiński Triangles by Molecular Puzzling

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