Fine-Tuning Electronic Properties of Luminescent Pt(II) Complexes via Vertex-Differentiated Coordination of Sterically Invariant Carborane-Based Ligands

We report the synthesis of two isomeric Pt(II) complexes ligated by doubly deprotonated 1,1′-bis(<i>o</i>-carborane) (<b>bc</b>). This work provides a potential route to fine-tune the electronic properties of luminescent metal complexes by virtue of vertex-differentiated coordination chemistry of carborane-based ligands

Metal-Free Peralkylation of the <i>closo</i>-Hexaborate Anion

The synthesis of fully alkylated <i>closo</i>-hexaborate dianions is reported. The reaction of [NBu₄]­[B₆H₆H^<i>fac</i>], benzyl bromide, and triethylamine under microwave heating conditions affords persubstituted [NBu₄]­[B₆(CH₂Ar)₆H^<i>fac</i>] (Ar = C₆H₅, 4–Br-C₆H₄), which have been isolated and characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, and other spectroscopic techniques. Electrochemical studies of these clusters reveal an irreversible one-electron oxidation, likely indicating degradative cage rupture. The observed metal-free alkylation is proposed to proceed as a consequence of the pronounced <i>nucleophilic</i> character of the hexaborate anion. This work represents the first example of a perfunctionalized hexaborate cluster featuring B–C bonds

Metal-Free Peralkylation of the <i>closo</i>-Hexaborate Anion

The synthesis of fully alkylated <i>closo</i>-hexaborate dianions is reported. The reaction of [NBu₄]­[B₆H₆H^<i>fac</i>], benzyl bromide, and triethylamine under microwave heating conditions affords persubstituted [NBu₄]­[B₆(CH₂Ar)₆H^<i>fac</i>] (Ar = C₆H₅, 4–Br-C₆H₄), which have been isolated and characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, and other spectroscopic techniques. Electrochemical studies of these clusters reveal an irreversible one-electron oxidation, likely indicating degradative cage rupture. The observed metal-free alkylation is proposed to proceed as a consequence of the pronounced <i>nucleophilic</i> character of the hexaborate anion. This work represents the first example of a perfunctionalized hexaborate cluster featuring B–C bonds

Metal-Free Peralkylation of the <i>closo</i>-Hexaborate Anion

The synthesis of fully alkylated <i>closo</i>-hexaborate dianions is reported. The reaction of [NBu₄]­[B₆H₆H^<i>fac</i>], benzyl bromide, and triethylamine under microwave heating conditions affords persubstituted [NBu₄]­[B₆(CH₂Ar)₆H^<i>fac</i>] (Ar = C₆H₅, 4–Br-C₆H₄), which have been isolated and characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, and other spectroscopic techniques. Electrochemical studies of these clusters reveal an irreversible one-electron oxidation, likely indicating degradative cage rupture. The observed metal-free alkylation is proposed to proceed as a consequence of the pronounced <i>nucleophilic</i> character of the hexaborate anion. This work represents the first example of a perfunctionalized hexaborate cluster featuring B–C bonds

Metal-Free Peralkylation of the <i>closo</i>-Hexaborate Anion

The synthesis of fully alkylated <i>closo</i>-hexaborate dianions is reported. The reaction of [NBu₄]­[B₆H₆H^<i>fac</i>], benzyl bromide, and triethylamine under microwave heating conditions affords persubstituted [NBu₄]­[B₆(CH₂Ar)₆H^<i>fac</i>] (Ar = C₆H₅, 4–Br-C₆H₄), which have been isolated and characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, and other spectroscopic techniques. Electrochemical studies of these clusters reveal an irreversible one-electron oxidation, likely indicating degradative cage rupture. The observed metal-free alkylation is proposed to proceed as a consequence of the pronounced <i>nucleophilic</i> character of the hexaborate anion. This work represents the first example of a perfunctionalized hexaborate cluster featuring B–C bonds

Chiral Reticular Chemistry: A Tailored Approach Crafting Highly Porous and Hydrolytically Robust Metal–Organic Frameworks for Intelligent Humidity Control

Control of humidity within confined spaces is critical for maintaining air quality and human well-being, with implications for environments ranging from international space stations and pharmacies to granaries and cultural relic preservation sites. However, existing techniques rely on energy-intensive electrically driven equipment or complex temperature and humidity control (THC) systems, resulting in imprecision and inconvenience. The development of innovative techniques and materials capable of simultaneously meeting the stringent requirements of practical applications holds the key to creating intelligent and energy-efficient humidity control devices. In this study, we introduce chiral reticular chemistry as a tailored synthetic approach, targeting a highly porous hea topological framework characterized by intrinsic interpenetrating pore architecture. This groundbreaking design successfully circumvents the traditional compromise between the pore volume and hydrolytic stability. Our metal–organic framework (MOF) exhibits an extraordinary working capacity, setting a new record at 1.35 g g–1 within the relative humidity (RH) range of 40–60%, without exhibiting hysteresis. Consequently, it emerges as a state-of-the-art candidate for intelligent humidity regulation within confined spaces. Utilizing single-crystal X-ray measurements and molecular simulations, we unequivocally elucidate the mechanism of water clustering and pore filling, underscoring the pivotal role of the linker functionality in governing the water seeding process. Our findings represent a significant advancement in the field, paving the way for the development of highly efficient humidity control technologies and offering promising solutions for diverse real-world scenarios

Chiral Reticular Chemistry: A Tailored Approach Crafting Highly Porous and Hydrolytically Robust Metal–Organic Frameworks for Intelligent Humidity Control

Control of humidity within confined spaces is critical for maintaining air quality and human well-being, with implications for environments ranging from international space stations and pharmacies to granaries and cultural relic preservation sites. However, existing techniques rely on energy-intensive electrically driven equipment or complex temperature and humidity control (THC) systems, resulting in imprecision and inconvenience. The development of innovative techniques and materials capable of simultaneously meeting the stringent requirements of practical applications holds the key to creating intelligent and energy-efficient humidity control devices. In this study, we introduce chiral reticular chemistry as a tailored synthetic approach, targeting a highly porous hea topological framework characterized by intrinsic interpenetrating pore architecture. This groundbreaking design successfully circumvents the traditional compromise between the pore volume and hydrolytic stability. Our metal–organic framework (MOF) exhibits an extraordinary working capacity, setting a new record at 1.35 g g–1 within the relative humidity (RH) range of 40–60%, without exhibiting hysteresis. Consequently, it emerges as a state-of-the-art candidate for intelligent humidity regulation within confined spaces. Utilizing single-crystal X-ray measurements and molecular simulations, we unequivocally elucidate the mechanism of water clustering and pore filling, underscoring the pivotal role of the linker functionality in governing the water seeding process. Our findings represent a significant advancement in the field, paving the way for the development of highly efficient humidity control technologies and offering promising solutions for diverse real-world scenarios

Programmed Polarizability Engineering in a Cyclen-Based Cubic Zr(IV) Metal–Organic Framework to Boost Xe/Kr Separation

Efficient separation of xenon (Xe) and krypton (Kr) mixtures through vacuum swing adsorption (VSA) is considered the most attractive route to reduce energy consumption, but discriminating between these two gases is difficult due to their similar properties. In this work, we report a cubic zirconium-based MOF (Zr-MOF) platform, denoted as NU-1107, capable of achieving selective separation of Xe/Kr by post-synthetically engineering framework polarizability in a programmable manner. Specifically, the tetratopic linkers in NU-1107 feature tetradentate cyclen cores that are capable of chelating a variety of transition-metal ions, affording a sequence of metal-docked cationic isostructural Zr-MOFs. NU-1107-Ag(I), which features the strongest framework polarizability among this series, achieves the best performance for a 20:80 v/v Xe/Kr mixture at 298 K and 1.0 bar with an ideal adsorbed solution theory (IAST) predicted selectivity of 13.4, placing it among the highest performing MOF materials reported to date. Notably, the Xe/Kr separation performance for NU-1107-Ag(I) is significantly better than that of the isoreticular, porphyrin-based MOF-525-Ag(II), highlighting how the cyclen core can generate relatively stronger framework polarizability through the formation of low-valent Ag(I) species and polarizable counteranions. Density functional theory (DFT) calculations corroborate these experimental results and suggest strong interactions between Xe and exposed Ag(I) sites in NU-1107-Ag(I). Finally, we validated this framework polarizability regulation approach by demonstrating the effectiveness of NU-1107-Ag(I) toward C3H6/C3H8 separation, indicating that this generalizable strategy can facilitate the bespoke synthesis of polarized porous materials for targeted separations

Blue Phosphorescent Zwitterionic Iridium(III) Complexes Featuring Weakly Coordinating <i>nido</i>-Carborane-Based Ligands

We report the development of a new class of phosphorescent zwitterionic <i>bis</i>(heteroleptic) Ir­(III) compounds containing pyridyl ligands with weakly coordinating <i>nido</i>-carboranyl substituents. Treatment of phenylpyridine-based Ir­(III) precursors with <i>C</i>-substituted <i>ortho</i>-carboranyl­pyridines in 2-ethoxyethanol results in a facile carborane deboronation and the formation of robust and highly luminescent metal complexes. The resulting <i>nido</i>-carboranyl fragments associate with the cationic Ir­(III) center through primarily electrostatic interactions. These compounds phosphoresce at blue wavelengths (450–470 nm) both in a poly­(methyl methacrylate) (PMMA) matrix and in solution at 77 K. These complexes display structural stability at temperatures beyond 300 °C and quantum yields greater than 40%. Importantly, the observed quantum yields correspond to a dramatic 10-fold enhancement over the previously reported Ir­(III) congeners featuring carboranyl-containing ligands in which the boron cluster is covalently attached to the metal. Ultimately, this work suggests that the use of a ligand framework containing a weakly coordinating anionic component can provide a new avenue for designing efficient Ir­(III)-based phosphorescent emitters

EvoEvo Deliverable 2.2 : Genome-network model

Genome-network model: Documented runnable genome-network model suitable for running in silico experiments. This model should follow the choices presented in deliverable 2.1