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1. Structural and electronic trends of optical cycling centers in polyatomic molecules revealed by microwave spectroscopy of MgCCH, CaCCH, and SrCCH

   https://doi.org/10.1073/pnas.2303586120  

   Changala, P Bryan; Genossar-Dan, Nadav; Brudner, Ella; Gur, Tomer; Baraban, Joshua H; McCarthy, Michael C (July 2023, Proceedings of the National Academy of Sciences)

   The unique optical cycling efficiency of alkaline earth metal–ligand molecules has enabled significant advances in polyatomic laser cooling and trapping. Rotational spectroscopy is an ideal tool for probing the molecular properties that underpin optical cycling, thereby elucidating the design principles for expanding the chemical diversity and scope of these platforms for quantum science. We present a comprehensive study of the structure and electronic properties in alkaline earth metal acetylides with high-resolution microwave spectra of 17 isotopologues of MgCCH, CaCCH, and SrCCH in their²Σ⁺ground electronic states. The precise semiexperimental equilibrium geometry of each species has been derived by correcting the measured rotational constants for electronic and zero-point vibrational contributions calculated with high-level quantum chemistry methods. The well-resolved hyperfine structure associated with the^1,2H,¹³C, and metal nuclear spins provides further information on the distribution and hybridization of the metal-centered, optically active unpaired electron. Together, these measurements allow us to correlate trends in chemical bonding and structure with the electronic properties that promote efficient optical cycling essential to next-generation experiments in precision measurement and quantum control of complex polyatomic molecules. 

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2. A Bridge too Far? Comparison of Transition Metal Complexes of Dibenzyltetraazamacrocycles with and without Ethylene Cross-Bridges: X-ray Crystal Structures, Kinetic Stability, and Electronic Properties

   https://doi.org/10.3390/molecules28020895  

   Walker, Ashlie N.; Ayala, Megan A.; Mondal, Somrita; Bergagnini, Mackenzie C.; Bui, Phuong John; Chidester, Stephanie N.; Doeden, Chad I.; Esjornson, Louise; Sweany, Brian R.; Garcia, Leslie; et al (January 2023, Molecules)

   Tetraazamacrocycles, cyclic molecules with four nitrogen atoms, have long been known to produce highly stable transition metal complexes. Cross-bridging such molecules with two-carbon chains has been shown to enhance the stability of these complexes even further. This provides enough stability to use the resulting compounds in applications as diverse and demanding as aqueous, green oxidation catalysis all the way to drug molecules injected into humans. Although the stability of these compounds is believed to result from the increased rigidity and topological complexity imparted by the cross-bridge, there is insufficient experimental data to exclude other causes. In this study, standard organic and inorganic synthetic methods were used to produce unbridged dibenzyl tetraazamacrocycle complexes of Co, Ni, Cu, and Zn that are analogues of known cross-bridged tetraazamacrocycles and their transition metal complexes to allow direct comparison of molecules that are identical except for the cross-bridge. The syntheses of the known tetraazamacrocycles and the new transition metal complexes were successful with high yields and purity. Initial chemical characterization of the complexes was conducted by UV-Visible spectroscopy, while cyclic voltammetry showed more marked differences in electronic properties from bridged versions. Direct comparison studies of the unbridged and bridged compounds’ kinetic stabilities, as demonstrated by decomposition using high acid concentration and elevated temperature, showed that the cyclen-based complex stability did not benefit from cross-bridging. This is likely due to poor complementarity with the Cu2+ ion while cyclam-based complexes benefited greatly. We conclude that ligand–metal complementarity must be maintained in order for the topological and rigidity constraints imparted by the cross-bridge to contribute significantly to complex robustness. 

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3. Bichromatic Imaging of Single Molecules in an Optical Tweezer Array

   https://doi.org/10.1103/PhysRevLett.131.053202  

   Holland, Connor M.; Lu, Yukai; Cheuk, Lawrence W. (August 2023, Physical Review Letters)

   We report on a novel bichromatic fluorescent imaging scheme for background-free detection of single CaF molecules trapped in an optical tweezer array. By collecting fluorescence on one optical transition while using another for laser cooling, we achieve an imaging fidelity of 97.7(2)% and a nondestructive detection fidelity of 95.5(6)%. Notably, these fidelities are achieved with a modest photon budget, suggesting that the method could be extended to more complex laser-coolable molecules with less favorable optical cycling properties. We also report on a framework and new methods to characterize various loss mechanisms that occur generally during fluorescent detection of trapped molecules, including two-photon decay and admixtures of higher excited states that are induced by the trapping light. In particular, we develop a novel method to dispersively measure transition matrix elements between electronically excited states. The method could also be used to measure arbitrarily small Franck-Condon factors between electronically excited states, which could significantly aid in ongoing efforts to laser cool complex polyatomic molecules. 

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4. Temperature-Dependent Spin-Driven Dimerization Determines the Ultrafast Dynamics of a Copper(II)-Bound Tripyrrindione Radical

   https://doi.org/10.1021/acs.jpclett.3c02726  

   Kumar, Anshu; Thompson, Benjamin; Gautam, Ritika; Tomat, Elisa; Huxter, Vanessa (December 2023, The Journal of Physical Chemistry Letters)

   Radicals and other open-shell molecules play a central role in chemical transformations and redox chemistry. While radicals are often highly reactive, stable radical systems are desirable for a range of potential applications, ranging from materials chemistry and catalysis to spintronics and quantum information. Here we investigate the ultrafast properties of a stable radical system with temperature-dependent spin-tunable properties. This radical complex, Cu(II) hexaethyl tripyrrin-1,14-dione, accommodates unpaired electrons localized on both the copper metal center and the tripyrrolic ligand. The unusual combination of two unpaired electrons and high stability in this radical molecule enable switchable temperature-dependent spin coupling. Two-dimensional electronic spectroscopy measurements of Cu(II) hexaethyl tripyrrin-1,14-dione were collected at room temperature and at 77 K. At room temperature, the molecules are present as monomers and have short picosecond lifetimes. At 77 K, the molecules are present in a dimer form mediated by ferromagnetic and antiferromagnetic coupling. This reversible spin-driven dimerization changes the optical properties of the system, generating long-lived excitonic states. 

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5. Microwave Absorption of Organic Metal Halide Nanotubes

   https://doi.org/10.1002/admi.201901270  

   Lin, Haoran; Green, Michael; Xu, Liang‐Jin; Chen, Xiaobo; Ma, Biwu (December 2019, Advanced Materials Interfaces)

   Abstract Organic metal halide hybrids have attracted tremendous research interests owing to their outstanding optical and electronic properties suitable for various applications, including photovoltaics, light‐emitting diodes, and photodetectors. Recently, the multifunctionality of this class of materials has been further explored beyond their optical and electronic properties. Here, for the first time the microwave electromagnetic properties of a 1D organic metal halide hybrid, (C₆H₁₃N₄)₃Pb₂Br₇, a single crystalline bulk assembly of organic metal halide nanotubes, are reported. Good microwave absorption performance with a large reflection loss value of −18.5 dB and a threshold bandwidth of 1.0 GHz is discovered for this material, suggesting its potential as a new microwave absorber. This work reveals a new functionality of organic metal halide hybrids and provides a new material class for microwave absorption application studies. 

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