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1. Construction of Janus dendrimers through a self-assembly approach involving chiral discrimination at a focal point

   https://doi.org/10.1039/D1CC01973B  

   Zhou, John; Cole, Ashley M.; Menuey, Elizabeth M.; Kilway, Kathleen V.; Moteki, Shin A. (June 2021, Chemical Communications)

   A strategy to build Janus dendrimers via the chirality-directed self-assembly of heteroleptic Zn( ii ) BOX complexes is reported. The method allows quantitative synthesis of Janus dendrimers in situ without the need for purifications. Each dendritic domain of the Janus dendrimers can be recycled upon disassembly at the focal point. 

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2. Cluster self-assembly and anion binding by metal complexes of non-innocent thiazolidinyl–thiolate ligands

   https://doi.org/10.1039/D2DT01339H  

   Riffel, Madeline N.; Siegel, Lukas; Oliver, Allen G.; Tsui, Emily Y. (June 2022, Dalton Transactions)

   Zn II and Fe II chloride complexes of a di(methylthiazolidinyl)pyridine ligand were deprotonated to form the corresponding thiolate complexes supported by redox-active iminopyridine moieties. The thiolate donor groups are nucleophilic and reactive toward oxidants, electrophiles, and protons, while the pendant thiazolidine rings are available for hydrogen bonding. Anion exchange with the weakly-coordinating triflate anion resulted in self-assembly of the iminopyridine complexes to form a trimeric [M 3 S 3 ] cluster. Hydrogen bonding closely associates anions with this trimetallic core. 

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3. Zinc(II) complexes of azadipyrromethene: Effect of nature and placement of solubilizing groups on structural, thermal, electrochemical and optical properties

   https://doi.org/10.1016/j.dyepig.2022.110858  

   Jimenez, Jayvic C.; Tran, Quynh; Pugh, Madison H.; Brancel, Christina D.; Rheingold, Arnold L.; Sauvé, Geneviève (January 2023, Dyes and Pigments)

   Zinc(II) complexes of azadipyrromethenes are non-planar chromophores with strong absorption in the visible to NIR and are promising n-type materials for organic solar cells. To increase solubility and tune their properties, we incorporated hexyl or hexyloxy solubilizing groups either on the distal or proximal phenyls of bis[2,6-diphenylethynyl-1,3,7,9-tetraphenyl azadipyrromethene] zinc(II) (Zn(WS3)2). Crystal structures confirm the typical distorted tetrahedral geometry for these types of complexes and show that the solubilizing groups on the distal phenyls extend away from the conjugated core whereas groups on proximal phenyls interact with the other ligand. Differential scanning calorimetry measurement indicated that crystals of distal-substituted complexes have two endothermic peaks: solubilizing groups ‘melting’ and complex melting, whereas the proximal substituted complexes show one exothermic crystallization peak and one endothermic melting peak. Electrochemical and optical properties varied as expected for ADP-based complexes: the presence of electron rich groups at the proximal substitutions resulted in lower oxidation potentials, higher HOMO levels, red-shifted absorption and lower optical gap than distal substitutions, and the effect was greater for hexyloxy than hexyl. Upon thermal annealing, films of the hexyloxy-substituted complexes strongly aggregated and showed crystal features under a polarized microscope, indicating that hexyloxy groups drive ordered self-assembly, especially when placed on distal phenyls. The ability to guide solid-state self-assembly of these non-planar chromophores using solubilizing groups have the potential to improve their charge carrier mobility and performance in opto-electronic applications such as organic solar cells, and photodetectors. 

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4. Formation of Microcages from a Collagen Mimetic Peptide via Metal-Ligand Interactions

   https://doi.org/10.3390/molecules26164888  

   Gleaton, Jeremy; Curtis, Ryan W.; Chmielewski, Jean (August 2021, Molecules)

   Here, the hierarchical assembly of a collagen mimetic peptide (CMP) displaying four bipyridine moieties is described. The CMP was capable of forming triple helices followed by self-assembly into disks and domes. Treatment of these disks and domes with metal ions such as Fe(II), Cu(II), Zn(II), Co(II), and Ru(III) triggered the formation of microcages, and micron-sized cup-like structures. Mechanistic studies suggest that the formation of the microcages proceeds from the disks and domes in a metal-dependent fashion. Fluorescently-labeled dextrans were encapsulated within the cages and displayed a time-dependent release using thermal conditions. 

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5. Pt(II)-Coordinated Tricomponent Self-Assemblies of Tetrapyridyl Porphyrin and Dicarboxylate Ligands: Are They 3D Prisms or 2D Bow-Ties?

   https://doi.org/10.1039/D1SC06533E  

   Benavides, Paola A.; Gordillo, Monica A.; Yadav, Ashok; Joaqui-Joaqui, M. Andrey; Saha, Sourav (March 2022, Chemical Science)

   Goldup, S (Ed.)

   Thermodynamically favored simultaneous coordination of Pt(II) corners with aza- and carboxylate ligands yields tricomponent coordination complexes with sophisticated structures and functions, which require careful structural characterization to paint accurate depiction of their structure–function relationships. Previous reports had claimed that heteroleptic coordination of cis-(Et3P)2PtII with tetrapyridyl porphyrins (M'TPP, M' = Zn or H2) and dicarboxylate ligands (XDC) yielded 3D tetragonal prisms containing two horizontal M'TPP faces and four vertical XDC pillars connected by eight Pt(II) corners, even though such structures were not supported by their 1H NMR data. Through extensive X-ray crystallographic and NMR studies, herein, we demonstrate that self-assembly of cis-(Et3P)2PtII, M'TPP, and four different XDC linkers having varied lengths and rigidity actually yields bow-tie (⋈)-shaped 2D [{cis-(Et3P)2Pt}4(M'TPP)(XDC)2]4+ complexes featuring a M'TPP core and two parallel XDC linkers connected by four heteroleptic PtII corners instead of 3D prisms. This happened because (i) irrespective of their length (~7–11 Å) and rigidity, the XDC linkers intramolecularly bridged two adjacent pyridyl-N atoms of a M'TPP core via PtII corners instead of connecting two cofacial M'TPP ligands and (ii) the bow-tie complexes are entropically more favored over prisms. The electron-rich ZnTPP core of a bow-tie complex selectively formed a charge-transfer complex with highly π-acidic 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-heaxacarbonitrile but not with a π-donor like pyrene. Thus, this work not only produced novel M'TPP-based bow-tie complexes and demonstrated their selective π-acid recognition capability, but also underscored the importance of proper structural characterization of supramolecular assemblies to ensure accurate depiction of their structure–property relationships. 

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