An official website of the United States government
Abstract Anionic ancillary ligands play a critical role in the construction of rare earth (RE) metal complexes due to the large influence on the stability of the molecule and engendering emergent electronic properties that are of interest in a plethora of applications. Supporting ligands comprising oxygen donor atoms are highly pursued in RE chemistry owing to the high oxophilicity innate to these ions. The scarcely employed bis(acyl)phosphide (BAP) ligands feature oxygen coordination sites and contain a phosphide backbone rendering it attractive for RE‐coordination chemistry. Here, we integrate bis(mesitoyl)phosphide (mesBAP) as an ancillary ligand into REIIIchemistry to generate the first dinuclear trivalent RE complexes containing BAP ligands; [{mesBAP}2RE(THF)(μ‐Cl)]2(RE=Y, (1), Gd (2), and Dy (3); THF=tetrahydrofuran). Each RE center is ligated to two monoanionicmesBAP ligands, one THF molecule and one chloride ion. All three molecules were characterized through single‐crystal X‐ray diffraction,31P NMR, IR and UV‐Vis spectroscopy.31P,1H and13C NMR on the diamagnetic yttrium congener1confirm asymmetric ligand coordination. DFT calculations conducted on2provided insight into the electronic structure. The magnetic properties of2and3were investigated via SQUID magnetometry. The GdIIIions exhibit weak antiferromagnetic coupling, corroborated by DFT results.
more »
« less
Antiferromagnetic Ordering in A One‐Dimensional Organic Copper Chloride Hybrid Insulator
Abstract Low dimensional (LD) organic metal halide hybrids (OMHHs) have recently emerged as new generation functional materials with exceptional structural and property tunability. Despite the remarkable advances in the development of LD OMHHs, optical properties have been the major functionality extensively investigated for most of LD OMHHs developed to date, while other properties, such as magnetic and electronic properties, remain significantly under‐explored. Here, we report for the first time the characterization of the magnetic and electronic properties of a 1D OMHH, organic‐copper (II) chloride hybrid (C8H22N2)Cu2Cl6. Owing to the antiferromagnetic coupling between Cu atoms through chloride bridges in 1D [Cu2Cl62−]∞chains, (C8H22N2)Cu2Cl6is found to exhibit antiferromagnetic ordering with a Néel temperature of 24 K. The two‐terminal (2T) electrical measurement on a (C8H22N2)Cu2Cl6single crystal reveals its insulating nature. This work shows the potential of LD OMHHs as a highly tunable quantum material platform for spintronics.
more »
« less
- PAR ID:
- 10544503
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 63
- Issue:
- 46
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
1D organic metal halide hybrids (OMHHs) exhibit strongly anisotropic optical properties, highly efficient light emission, and large Stokes shift, holding promise for novel photodetection and lighting applications. However, the fundamental mechanisms governing their unique optical properties and in particular the impacts of surface effects are not understood. Herein, 1D C4N2H14PbBr4by polarization‐dependent time‐averaged and time‐resolved photoluminescence (TRPL) spectroscopy, as a function of photoexcitation energy, is investigated. Surprisingly, it is found that the emission under photoexcitation polarized parallel to the 1D metal halide chains can be either stronger or weaker than that under perpendicular polarization, depending on the excitation energy. The excitation‐energy‐dependent anisotropic emission is attributed to fast surface recombination, supported by first‐principles calculations of optical absorption in this material. The fast surface recombination is directly confirmed by TRPL measurements, when the excitation is polarized parallel to the chains. The comprehensive studies provide a more complete picture for a deeper understanding of the optical anisotropy in 1D OMHHs.more » « less
-
Abstract Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (1, M=Co,2: M=Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single‐crystal X‐ray diffraction structure analysis. The isostructural clusters are formed of edge‐sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of1and2in an unusual two‐mode fashion, unobserved previously. In the crystalline state, the clusters of1and2are joined by hydrogen bonds to form a three‐dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [Jiso(VIV−VIV)=−5.4(1); −3.9(2) cm−1], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [Jiso(VIV−CoII)=−12.6 and −7.5 cm−1] contained in1.more » « less
-
Tailorable Multi‐Modular Pore‐Space‐Partitioned Vanadium Metal‐Organic Frameworks for Gas SeparationAbstract Currently, few porous vanadium metal‐organic frameworks (V‐MOFs) are known and even fewer are obtainable as single crystals, resulting in limited information on their structures and properties. Here this work demonstrates remarkable promise of V‐MOFs by presenting an extensible family of V‐MOFs with tailorable pore geometry and properties. The synthesis leverages inter‐modular synergy on a tri‐modular pore‐partitioned platform. New V‐MOFs show a broad range of structural features and sorption properties suitable for gas storage and separation applications for C2H2/CO2, C2H6/C2H4, and C3H8/C3H6. Thec/aratio of the hexagonal cell, a measure of pore shape, is tunable from 0.612 to 1.258. Other tunable properties include pore size from 5.0 to 10.9 Å and surface area from 820 to 2964 m2g−1. With C2H2/CO2selectivity from 3.3 to 11 and high uptake capacity for C2H2from 65.2 to 182 cm3g−1(298K, 1 bar), an efficient separation is confirmed by breakthrough experiments. The near‐record high uptake for C2H6(166.8 cm3g−1) contributes to the promise for C2H6‐selective separation of C2H6/C2H4. The multi‐module pore expansion enables transition from C3H6‐selective to more desirable C3H8‐selective separation with extraordinarily high C3H8uptake (254.9 cm3g−1) and high separation potential (1.25 mmol g−1) for C3H8/C3H6(50:50 v/v) mixture.more » « less
-
Gas‐Induced Electrical and Magnetic Modulation of Two‐Dimensional Conductive Metal–Organic FrameworkAbstract Controlled modulation of electronic and magnetic properties in stimuli‐responsive materials provides valuable insights for the design of magnetoelectric or multiferroic devices. This paper demonstrates the modulation of electrical and magnetic properties of a semiconductive, paramagnetic metal−organic framework (MOF) Cu3(C6O6)2with small gaseous molecules, NH3, H2S, and NO. This study merges chemiresistive and magnetic tests to reveal that the MOF undergoes simultaneous changes in electrical conductance and magnetization that are uniquely modulated by each gas. The features of response, including direction, magnitude, and kinetics, are modulated by the physicochemical properties of the gaseous molecules. This study advances the design of multifunctional materials capable of undergoing simultaneous changes in electrical and magnetic properties in response to chemical stimuli.more » « less
