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p-Donor/Acceptor charge-transfer (CT) interactions between redox-complementary p-systems often give rise to non-native optical and electronic properties that are beneficial for modern electronics and energy technologies. However, the formation of extended supramolecular p-donor/acceptor stacks capable of long-range charge transport requires ingenious design strategies that can help reinforce otherwise weak p-donor/acceptor noncovalent interactions. Herein, we demonstrate that a large tetragonal prismatic metal–organic cage (MOC28+) having two parallel p-donor tetrakis(4- carboxyphenyl)-Zn-porphyrin (ZnTCPP) faces located B14 Å apart can accommodate up to three redox-complementary planar aromatic guests (either three p-acceptor guests or two p-acceptors surrounding one p-donor guest) between the ZnTCPP faces, forming extended p-donor/acceptor stacks. While empty MOC28+ behaves as an insulator due to the lack of charge delocalization across its large cavity, its inclusion complexes saturated with p-acidic hexaazatriphenylene hexacarbonitrile (HATHCN) and hexacyanotriphenylene (HCTP) displayed noticeably higher electrical conductivity (8.7   10 6 and 1.3   10 6 S m 1, respectively) owing to more facile charge transport through the p-donor/ acceptor stacks composed of the p-acidic guests intercalated between the ZnTCPP faces. Thus, this work demonstrates that tetragonal prismatic metallacages with two parallel electroactive faces can facilitate the creation of extended p-donor/acceptor stacks by encapsulating redox-complementary planar guests, which in turn facilitates through-space charge delocalization, generating non-native electrical conductivity. 

Abstract. We introduce physics-informed multimodal autoencoders (PIMA) - a variational inference framework for discovering shared information in multimodal datasets. Individual modalities are embedded into a shared latent space and fused through a product-of-experts formulation, enabling a Gaussian mixture prior to identify shared features. Sampling from clusters allows cross-modal generative modeling, with a mixture-of-experts decoder that imposes inductive biases from prior scientific knowledge and thereby imparts structured disentanglement of the latent space. This approach enables cross-modal inference and the discovery of features in high-dimensional heterogeneous datasets. Consequently, this approach provides a means to discover fingerprints in multimodal scientific datasets and to avoid traditional bottlenecks related to high-fidelity measurement and characterization of scientific 

Abstract Due to their diverse potential in advanced electronics and energy technologies, electrically conducting metal‐organic frameworks (MOFs) are drawing significant attention. Although hexagonal 2D MOFs generally display impressive electrical conductivity because of their dual in‐plane (through bonds) and out‐of‐plane (through π‐stacked ligands) charge transport pathways, notable differences between these two orthogonal conduction routes cause anisotropic conductivity and lower bulk conductivity. To address this issue, we have developed the first redox‐complementary dual‐ligand 2D MOF Cu₃(HHTP)(HHTQ), featuring a π‐donor hexahydroxytriphenylene (HHTP) ligand and a π‐acceptor hexahydroxytricycloquinazoline (HHTQ) ligand located at alternate corners of the hexagons, which form either parallel HHTP and HHTQ stacks (AA stacking) or alternating HHTP/HHTQ stacks (AB stacking) along the c‐axis. Regardless of the stacking pattern, Cu₃(HHTP)(HHTQ) supports more effective out‐of‐plane conduction through either separate π‐donor and π‐acceptor stacks or alternating π‐donor/acceptor stacks, while promoting in‐plane conduction through the pushpull‐like heteroleptic coordination network. As a result, Cu₃(HHTP)(HHTQ) exhibits higher bulk conductivity (0.12 S/m at 295 K) than single‐ligand MOFs Cu₃(HHTP)₂(7.3 × 10⁻²S/m) and Cu₃(HHTQ)₂(5.9 × 10⁻⁴S/m). This work introduces a new design approach to improve the bulk electrical conductivity of 2D MOFs by supporting charge transport in both in‐ and out‐of‐plane direcations. 

Novel columnar lanthanide metal–organic frameworks (Ln-MOFs) based on a butterfly-shaped electron-rich π-extended tetrathia-fulvalene ligand (ExTTFTB) were synthesized and their electronic properties were investigated. Upon iodine-induced ligand oxidation, the Tb-MOF displayed ca. 100-fold higher electrical conductivity (5 × 10 −7 S m −1 ) than the neutral pristine MOF. 

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.