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• Handzlik, G., Ligiel Relaxing amid Three: Slow Magnetization Relaxation in Three-Coordinate Chromium(II) N-Heterocyclic Carbene Complexes Chem. Eur. J.  , 2025 , , e202500607.

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Relaxing amid Three: Slow Magnetization Relaxation in Three-Coordinate Chromium(II) N-Heterocyclic Carbene Complexes

Authors:Handzlik, G., Ligielli, I., Nain, S., Khurana, R., Ali, M.E., Papangelis, E., Papapanagis, C., Bailly, C., Tsoureas, N., Danopoulou, M. and Bethanis, C.

Publication Details:Chem. Eur. J. ,2025, , e202500607

Abstract:
Three-coordinate, paramagnetic Cr^II complexes of type [Cr(amido)_nBn_m(NHC)], NHC = N, N’-bis-(2,4,6-trimethylphenyl)-imidazol-2-ylidene (IMes); N, N’-bis-(2,6-di-isopropylphenyl)-imidazol(in)-2-ylidene, (S)IDiPP; N, N’-bis-(2,6-di-isopropylphenyl)-imidazol-4-ylidene, (aIDiPP); amido = N(SiMe₃)₂, NH(DiPP); Bn = benzyl, n = 2, m = 0; n = 1, m = 1, were prepared by substitution or aminolysis and thermolysis methods from [Cr{N(SiMe₃)₂}₂(THF)₂] or [CrBn₂((S)IDiPP)], respectively. Depending on the nature of the NHC and the amido ligands, different geometries at Cr^II (ranging from distorted trigonal planar, to extended Y-, compressed Y-, and distorted T-shaped) and conformations, were observed. HFEPR spectroscopy was employed to accurately determine spin Hamiltonian parameters, consisting of zero-field splitting (axial D and rhombic E components) and g-values, of five S = 2 complexes exhibiting D and E/D in the range from −2.98 to −1.63 cm⁻¹ and 0.026 − 0.069, respectively. AC magnetometry established slow magnetization relaxation in three complexes, operating by Raman or combined Raman-Orbach processes. Ab initio calculations provided computed zfs values, in good agreement with those obtained by HFEPR. Magnetostructural comparisons are made within this three-coordinate Cr^II family, as well as with previously studied two- or four- coordinate Cr^II complexes.

DOI Link: 10.1002/chem.202500607

• Bhunia, N., Ali, S., Identification of Cosensitizers for Triggering Terbium Emission Enhancement in Zinc Sulfide Nanoparticles ACS Appl. Opt. Mater..  , 2025 , , .

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Identification of Cosensitizers for Triggering Terbium Emission Enhancement in Zinc Sulfide Nanoparticles



Authors:Bhunia, N., Ali, S., Bhar, M., Debnath, G.H., Ali, M.E. and Mukherjee, P.

Publication Details:ACS Appl. Opt. Mater.. ,2025, ,

Abstract:


This study uses precation exchange reactions to gauge terbium emission enhancement through cosensitization effects in Zn(Tb)S NPs that are modified postsynthetically by Pb²⁺, Sn²⁺, Sn⁴⁺, Sb³⁺, Bi³⁺, In³⁺, and Tl⁺ to generate Zn(Tb)S/M (Mⁿ⁺ = Pb²⁺, Sn²⁺, Sn⁴⁺, Sb³⁺, Bi³⁺, In³⁺, and Tl⁺) NPs. Mⁿ⁺-induced cosensitization of Tb³⁺ emission is observed in the Sn²⁺, Pb²⁺, and Sb³⁺-containing NPs, with [Zn(Tb)S]: [Mⁿ⁺] = 1:10^–2. Tl⁺ produces similar sensitized emission in the NPs, however, only when the amount of these cations is in stoichiometric excess. On the contrary, the NPs with Sn⁴⁺, Bi³⁺, and In³⁺ do not provide such sensitization. The electronic cross-talk in these codopant(s) leading to cosensitization effects is correlated with the placement of codopant energy levels in the host NPs from the density functional theory calculations. The results collectively offer a rationale for predicting the appropriate codopant–Tb³⁺ (donor–acceptor) pair to achieve favorable electronic interactions that cosensitize Tb³⁺ emission in Zn(Tb)S/M NPs. Such Tb³⁺ emission enhancements create inroads for applications in sensing and imaging.

DOI Link: 10.1021/acsaom.5c00129

• Mahanta, S.P.; Sahoo Spinterface-Mediated Magnetic Properties of Nanoscale-Thick Co20Fe60B20/Alq3 Heterostructures for Spintronic Applications ACS Appl. Nano Mater. , 2025 , 8 , .

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Spinterface-Mediated Magnetic Properties of Nanoscale-Thick Co20Fe60B20/Alq3 Heterostructures for Spintronic Applications



Authors:Mahanta, S.P.; Sahoo, A.; Mukhopadhyaya, A.; Nayak, S.; Hase, T.P., Ali, M.E.; Atkinson, D. and Bedanta, S.

Publication Details:ACS Appl. Nano Mater.,2025, 8,

Abstract:
Organic semiconductors (OSCs) are suitable materials for spintronic applications as they can form a “spinterface” when placed next to a ferromagnetic layer, which in turn leads to emerging functionalities. The electronic interactions across the interface can impact the overall magnetic anisotropy, the magnetization reversal, and the magnetization dynamics of the ferromagnet/OSC heterostructure. Planar tris(8-hydroxy- quinoline)aluminum (Alq₃) OSC has shown tremendous potential for spintronics applications thanks to its efficient spin-polarized current transport ability. Here, we study the effects of the hybrid interface formed at the nanoscale when Alq₃ molecules are deposited onto a native amorphous ferromagnet Co₂₀Fe₆₀B₂₀ (CFB) layer. The π-d hybridization in CFB/Alq₃ enhances the coercive field and significantly modifies the shape and size of the magnetic domains. An ∼86% increase in uniaxial anisotropic energy and a reduction in magnetic damping are also evidence of the formation of interfacial hybrid states. The noncollinear density functional theory calculations on the proximal model systems show a modification in the local magnetic anisotropies due to molecular decoration in the model ferromagnetic substrates.

DOI Link: 10.1021/acsanm.5c01684

• Chibh, S., Aggarwal, Photoresponsive and Shape-Switchable MoS2–Peptide-Hybrid Nanosystems for Enacting Photochemo and siRNA-Mediated Gene Therapy in Glioma J. Phys. Chem. B.  , 2025 , 17 , 29318-29340.

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Photoresponsive and Shape-Switchable MoS2–Peptide-Hybrid Nanosystems for Enacting Photochemo and siRNA-Mediated Gene Therapy in Glioma



Authors:Chibh, S., Aggarwal, N., Gupta, N., Ali, S., Mishra, J., Tiwari, S., Ali, M.E., Mishra, D.P. and Panda, J.J.

Publication Details:J. Phys. Chem. B. ,2025, 17, 29318-29340

Abstract:
Exfoliated 2D transition-metal dichalcogenide (TMDCs)-based nanomaterials have captured a huge biomedical territory owing to their supreme physicochemical properties. However, the tedious and harsh chemical exfoliation of bulk MoS₂ impacts its utility in the biological domain. The study introduces a facile and environmentally benign way of shape-tunable exfoliation of bulk MoS₂ materials in an aqueous dispersion using designed self-assembled, tetrapeptide (Fmoc-HCKF–OH)-based nanostructures, generating hybrid MoS₂-peptide nanosystems for both tumor-targeted [employing folic acid (FA) functionalization] and NIR-responsive delivery of anticancer siRNA/drug in glioma. Exfoliated MoS₂-peptide NSs here prove to be an excellent photothermal agent by inducing a temperature elevation upto ∼51 °C upon 808 nm NIR absorption. Enhanced siRNA/Dox loading onto the 2D flat morphology of MoS₂-peptide NSs resulted in ∼90% cancer cell death in C6 glioma cells under NIR exposure. The expression of the Galectin-1 oncogene was suppressed following the treatment. Thereafter, analysis in the C6 glioma syngeneic rat model demonstrated a significant reduction (>10 fold) in tumor volume with siRNA/Dox-loaded FA-MoS₂-peptide NSs + NIR as compared to the phosphate buffer saline-treated control group. Further, in vivo biodistribution studies confirmed the higher targetability of FA-conjugated hybrid NSs. Taken together, our findings promote the utility of TMDC-based nanomaterials in conjecture with a biocompatible peptide scaffold as a trimodal chemo, gene, and phototherapeutic agent.

DOI Link: 10.1021/acsami.5c03616

• Das, S.; Monika, Ali Harnessing Renewable Energy via Tunable Hydrovoltaic Power Generation on Cobalt Intercalated Nitrogen-doped Graphene Adv. Energy Mater. , 2025 , , e202500607.

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Harnessing Renewable Energy via Tunable Hydrovoltaic Power Generation on Cobalt Intercalated Nitrogen-doped Graphene

Authors:Das, S.; Monika, Ali, S.; Rani, D.; EM, H.; Bhardwaj, P.; Siddiqui, S.A.; Afshan, M., Rani, S.; Chaudhary, N. and Sharangi, S.

Publication Details:Adv. Energy Mater.,2025, , e202500607

Abstract:
With the increasing demand and rising environmental adulteration, researchers are exploring sustainable energy harvesting methods. Water-based energy harvesting using carbonaceous matrices and 2D layered materials has gained significant attention due to their superior electrical properties at low-dimension. This study demonstrates cobalt-nitrogen-doped graphene (Co-N-Gr) thin layers are presented as an efficient medium for harvesting energy from diverse water sources, including simulated seawater (0.6m NaCl), rainwater, and for differentiating pH levels and detecting acidic contaminants (H₂SO₄ and HNO₃) in the aquatic environment. The nitrogen-functionalized graphene-assisted cobalt immobilization enhances power generation by ≈108 times compared to pristine graphene (P-Gr) without any secondary heterojunction materials. The Co-N-Gr matrix improves hydrophilicity, facilitating ionic interaction and charge transfer, achieving ≈2.7 nW power generation under drop-by-drop motion of DI water. A mechanistic understanding is developed through experimental findings supported by density functional theory calculation to identify the role of anionic (Cl⁻ and F⁻) interaction via electrical double-layer formation. The selective higher interaction energy with HNO₃ leads to four times higher power generation than H₂SO₄ at the same concentration, highlighting its potential for the integration of renewable energy harvesting along with rain quality detection onto a single platform for developing commercialized smart windows.

DOI Link: 10.1002/aenm.202500138

• Panday, R.R.; Ali, S An electron rich triazine-based covalent organic framework as an aqueous electrolyte symmetric supercapacitor CHEMCOM , 2025 , 61 , 7831-7834.

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An electron rich triazine-based covalent organic framework as an aqueous electrolyte symmetric supercapacitor

Authors:Panday, R.R.; Ali, S.; Ali, M.E.; Kalla, S.; Pandey, R.K. and Jangir, R

Publication Details:CHEMCOM,2025, 61, 7831-7834

Abstract:
A novel covalent organic framework (COF), TDMTA-TFP-COF, was synthesized through the condensation of a triazine-based triamine with triformyl phloroglucinol for supercapacitor electrode applications. It demonstrated remarkable specific capacitance, energy density, and power density in both three-electrode and symmetric supercapacitor configurations. This study highlights the potential of TDMTA-TFP-COF as a promising electrode material for energy storage applications.

DOI Link: 10.1039/D5CC01105A

• Bajaj, A.; Ali, S.; Quantum Spin Transport Through Blatter’s Diradicals and Triradicals J. Phys. Chem. B.  , 2025 , 129 , 4252-4264.

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Quantum Spin Transport Through Blatter’s Diradicals and Triradicals



Authors:Bajaj, A.; Ali, S.; Khurana, R. and Ali, M.E.

Publication Details:J. Phys. Chem. B. ,2025, 129, 4252-4264

Abstract:
A single unpaired electron in an organic molecule residing in the singly occupied molecular orbital (SOMO) renders it an organic radical. It incorporates exchange splitting in the frontier occupied and unoccupied orbitals, separating the α- and β-orbitals. This fact enormously impacts the electron transport properties in organic radicals by promoting spin-polarized current and significantly enhancing conductance compared to their closed-shell counterparts. Exploring these phenomena, several monoradicals have been investigated through molecular spintronic experiments and theories. In this work, we addressed the impact of an increasing number of radical centers on the transport properties of multiradical molecular species by considering di- and triradicals based on a stable Blatter’s radical. With an increasing number of radical centers, the number of SOMOs increases. Does the increased number of frontier SOMOs provide larger exchange splitting and better transport properties? Here, we observed that the spatial distributions of SOMOs and their coupling with electrodes play a decisive role compared with the presence of multiple unpaired electrons in the molecular systems.

DOI Link: 10.1021/acs.jpca.4c08702

• Sharma, P.; Yuan, H. Intrinsically Pro‐Apoptotic Gold Nanoclusters for Optical Tracing and Inhibition of Solid Tumors Adv. Healthc. Mater. , 2025 , , .

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Intrinsically Pro‐Apoptotic Gold Nanoclusters for Optical Tracing and Inhibition of Solid Tumors

Authors:Sharma, P.; Yuan, H.; Verma, R.; Mehla, N.; Hemant, H.; Sagar, P.; Comby‐Zerbino, C.; Russier‐Antoine, I.; Moulin, C.; Brevet, P.F. and Singhal, N.

Publication Details: Adv. Healthc. Mater.,2025, ,

Abstract:
Intrinsically theranostic metal nanoclusters are rare unless the stabilizing ligands exhibit therapeutic properties. A promising class of quasi-molecular, near-infrared (NIR) emitting, cytotoxic gold nanoclusters, coined as AXE (Au eXcitable and Eliminable) stabilized through terminal thioester groups on fluorinated, and crosslinked polymers, is presented for simultaneous bioimaging & therapy. Nano Variable Temperature-Electrospray ionization mass spectrometry analysis of these aqueous stable nanoclusters revealed 5 to 7 core gold atoms, with SAXS measurement confirming average size to be under 1 nm, consistent with the theoretical maximum for few atom planar gold clusters. Despite its small size, AXE exhibits a remarkable Stoke shift of ≈470 nm and emission range spanning 700 to 1100 nm. Fluorination notably enhanced the quantum yield by up to twofold, attributed to charge transfer from the fluorinated monomer to the gold core, as indicated by Löwdin charge distribution analysis. The AXE nanocluster demonstrated dose-dependent pro-apoptotic effects on cancer cells while sparing normal cells at lower concentrations. Preclinical evaluation in a breast tumor model confirmed its anticancer efficacy, with intravenous and intraperitoneal administrations significantly inhibiting tumor growth and controlling lung metastasis, surpassing the clinical standard, doxorubicin.

DOI Link: 10.1002/adhm.202405005

• Ali, S. and Ali, M.E Quantum spin sensors for open-shell molecules J. Mater. Chem. C. , 2025 , 13 , 7760-7771.

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Quantum spin sensors for open-shell molecules



Authors:Ali, S. and Ali, M.E.

Publication Details: J. Mater. Chem. C.,2025, 13, 7760-7771

Abstract:


Zigzag graphene nanoribbons (ZGNRs) exhibit symmetric, but opposite spin distributions on their edges, making them susceptible to perturbations due to molecular adsorption. This study investigates the impact of the adsorption of closed-shell (e.g. N₂, CO, CO₂) and open-shell paramagnetic (e.g. O₂, NO, NO₂) molecules on the spin-polarized quantum transport properties of zigzag graphene nanoribbons using density functional theory and nonequilibrium Green's function (NEGF-DFT) methods. We found that closed-shell molecules physisorbed on graphene nanoribbons, while open-shell molecules chemisorbed strongly at the edges. This chemisorption disrupts the symmetric spin distribution, leading to spin-polarized transmission. The underlying mechanism for spin-polarized transmission in open-shell molecule adsorption cases is the quantum interference between the localized and delocalized hybridized states of molecule adsorbed graphene nanoribbons. The analysis of bond current, the current between a pair of two atoms, shows that physisorbed closed-shell molecules act as a scattering center, which reduces the current through graphene nanoribbons. We showed that the interaction of open-shell molecules with the graphene nanoribbons depends on the electronic properties of adsorbed molecules. Thus, a variation in the destructive quantum interference pattern is observed for different open-shell molecules resulting in different spin currents. This phenomenon can be used for molecular recognition of open-shell paramagnetic species, providing avenues for quantum spin sensor technology.

DOI Link: 10.1039/D4TC04667F

• Nath, A.R.; Kumar, M Intramolecular Magnetic Exchange Interaction in Dichalcogenide Substituted Organic Diradical Dications J. Chem. Theory Comput . , 2025 , 21 , 1507-2152.

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Intramolecular Magnetic Exchange Interaction in Dichalcogenide Substituted Organic Diradical Dications



Authors:Nath, A.R.; Kumar, M. and Ali, M.E.

Publication Details: J. Chem. Theory Comput .,2025, 21, 1507-2152

Abstract:
Organic diradical dications, due to reduced intermolecular interactions, exhibit a greater tendency to adopt high spin states in the solid phase compared to their neutral diradical counterparts. This characteristic makes them promising candidates for applications involving organic electronics. We present a theoretical study of a recently synthesized sulfur-based diradical dication, a unique system exhibiting a robust triplet ground state. Using a number of density functional theory (DFT)-based methods (e.g., standard broken-symmetry DFT, constrained DFT, spin-flip TDDFT) and wave function-based multireference CASSCF+NEVPT2 methods, we investigate its magnetic properties and explore the influence of chalcogen substitution on magnetic exchange coupling. An active space scanning method was adopted to overcome the difficulties in choosing the correct active space for multireference calculation. Our findings highlight the critical role of multireference methods in accurately capturing the magnetic behavior of highly π-conjugated systems. The study reveals a surprising variation in magnetic properties among sulfur, selenium, and tellurium-based diradical dications despite being elements of the same group. These results offer valuable insights into the design and tuning of magnetic properties in organic diradical dications.

DOI Link: 10.1021/acs.jctc.4c01505