The rise of metal–organic polyhedra

Lee, Soochan; Jeong, Hyein; Nam, Dongsik; Lah, Myoung Soo; Choe, Wonyoung

doi:10.1039/d0cs00443j

Cited by 175 publications

(161 citation statements)

References 189 publications

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“…This ligand displays a bent angle of α = 149°. [27] Heating a mixture of L1 (1 equiv), L5 (1 equiv), and [Pd(CH 3 CN) 4 ](BF 4 ) 2 (1 equiv) in CD 3 CN to 70°C for 7 days gave again a defined assembly, as evidenced by 1 H and DOSY NMR spectroscopy (Figures S23-S26). However, the HRMS data suggested that a hexanuclear instead of a tetranuclear complex had formed (Figure S27).…”

Section: Resultsmentioning

confidence: 92%

“…All these parameters can influence the self-assembly reaction. [1][2][3][4][5][6][7][8][9][10][11] Evidently, the reaction partner needs to be taken into account, and the ligand should be a good match for the corresponding metal ion (or complex).…”

Section: Introductionmentioning

confidence: 99%

“…Important ligand characteristics are size, geometry, rigidity, nature of the donor atoms, denticity, charge, and steric demand. All these parameters can influence the self‐assembly reaction [1–11] . Evidently, the reaction partner needs to be taken into account, and the ligand should be a good match for the corresponding metal ion (or complex).…”

Section: Introductionmentioning

confidence: 99%

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Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle

Fadaei‐Tirani

Scopelliti

et al. 2021

Chemistry A European J

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Spherical assemblies of the type [Pd n L 2n ] 2n + can be obtained from Pd II salts and curved N-donor ligands, L. It is well established that the bent angle, α, of the ligand is a decisive factor in the self-assembly process, with larger angles leading to complexes with a higher nuclearity, n. Herein, we report heteroleptic coordination cages of the type [Pd n L n L' n ] 2n + , for which a similar correlation between the ligand bent angle and the nuclearity is observed. Tetranuclear cages were obtained by combining [Pd(CH 3 CN) 4 ](BF 4 ) 2 with 1,3-di(pyridin-3-yl)benzene and ligands featuring a bent angle of α = 120°. The use of a dipyridyl ligand with α = 149°led to the formation of a hexanuclear complex with a trigonal prismatic geometry; for linear ligands, octanuclear assemblies of the type [Pd 8 L 8 L' 8 ] 16 + were obtained. The predictable formation of heteroleptic Pd II cages from 1,3-di(pyridin-3-yl) benzene and different dipyridyl ligands is evidence that there are entire classes of heteroleptic cage structures that are privileged from a thermodynamic point of view.

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Section: Resultsmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle

Fadaei‐Tirani

Scopelliti

et al. 2021

Chemistry A European J

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“…The attractive properties of MOFs have largely been underpinned by important design principles surrounding their net topology ( Robson 2000 ), isoreticular chemistry ( Furukawa et al, 2013 ), and post-synthetic chemistry ( Mandal et al, 2021 ). Over the past decade, it has been demonstrated that discrete molecular compounds, such as porous organic cages and metal-organic cages (MOCs), possess many of the attractive properties of MOFs ( Hasell and Cooper, 2016 ; Lee et al, 2021 ; Pullen and Clever, 2018 ). Unlike MOFs, MOCs are inherently soluble, and this characteristic opens up avenues for solution processing and hybridization with organic polymers ( Pastore and Cook, 2020 ).…”

Section: Introductionmentioning

confidence: 99%

Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage

et al. 2021

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The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu4L4 lantern cage (1). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units (2). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer (3) via imine condensation.

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“…The structural directing role of the bridging ligand as a non-metallic inverse coordination center (centroligand) is the cornerstone of the ICC viewpoint. Moreover, it is ultimately responsible for the magnetic properties of a unique class of IPCs and ICPs with paramagnetic 3d–5d metal ions that behave as molecular nanomagnets and molecule-based magnets [ 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. They include discrete metal-fluoride rings [ 25 , 26 , 27 , 28 ], metal-oxo clusters [ 29 , 30 , 31 ], and metal-cyanide polyhedra [ 32 ], as well as a variety of chains, layers, and different networks with cyanide [ 33 , 34 ] and polycyanocarbon anion radicals [ 35 , 36 ].…”

Section: Introductionmentioning

confidence: 99%

Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives

et al. 2021

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Two novel copper(II) complexes of formulas {[Cu(4-Hmpz)4][Cu(4-Hmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(ClO4)2]}n (1) and {[Cu(3,4,5-Htmpz)4]2[Cu(3,4,5-Htmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(H2O)(ClO4)]2[Cu2(3,4,5-Htmpz)4(µ-ox-κ2O1,O2:κ2O2′,O1′)]}(ClO4)4·6H2O (2) have been obtained by using 4-methyl-1H-pyrazole (4-Hmpz) and 3,4,5-trimethyl-1H-pyrazole (3,4,5-Htmpz) as terminal ligands and oxalate (ox) as the polyatomic inverse coordination center. The crystal structure of 1 consists of perchlorate counteranions and cationic copper(II) chains with alternating bis(pyrazole)(µ3-κ2O1,O2:κO2′:κO1′-oxalato)copper(II) and tetrakis(pyrazole)copper(II) fragments. The crystal structure of 2 is made up of perchlorate counteranions and cationic centrosymmetric hexanuclear complexes where an inner tetrakis(pyrazole)(µ-κ2O1,O2:κ2O2′,O1′-oxalato)dicopper(II) entity and two outer mononuclear tetrakis(pyrazole)copper(II) units are linked through two mononuclear aquabis(pyrazole)(µ3-κ2O1,O2:κO2′:κO1′-oxalato)copper(II) units. The magnetic properties of 1 and 2 were investigated in the temperature range 2.0–300 K. Very weak intrachain antiferromagnetic interactions between the copper(II) ions through the µ3-ox-κ2O1,O2:κO2′:κO1′ center occur in 1 [J = −0.42(1) cm−1, the spin Hamiltonian being defined as H = −J∑S1,i · S2,i+1], whereas very weak intramolecular ferromagnetic [J = +0.28(2) cm−1] and strong antiferromagnetic [J’ = −348(2) cm−1] couplings coexist in 2 which are mediated by the µ3-ox-κ2O1,O2:κO2′:κO1′ and µ-ox-κ2O1,O2:κ2O2′,O1′ centers, respectively. The variation in the nature and magnitude of the magnetic coupling for this pair of oxalato-centered inverse copper(II) complexes is discussed in the light of their different structural features, and a comparison with related oxalato-centered inverse copper(II)-pyrazole systems from the literature is carried out.

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The rise of metal–organic polyhedra

Abstract: Metal–organic polyhedra (MOPs) are comprehensively summarized and classified based on topology, providing new directions for MOP design and forthcoming applications.

Cited by 175 publications

References 189 publications

Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle

Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle

Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage

Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives

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