@article{chen_pedersen_dow_fayad_hauke_rosko_danilov_blakemore_dechert-schmitt_knauber_et al._2022, title={A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids}, volume={144}, ISSN={["1520-5126"]}, url={http://dx.doi.org/10.1021/jacs.2c02392}, DOI={10.1021/jacs.2c02392}, abstractNote={Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. We leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.}, number={18}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, publisher={American Chemical Society (ACS)}, author={Chen, Tiffany Q. and Pedersen, P. Scott and Dow, Nathan W. and Fayad, Remi and Hauke, Cory E. and Rosko, Michael C. and Danilov, Evgeny O. and Blakemore, David C. and Dechert-Schmitt, Anne-Marie and Knauber, Thomas and et al.}, year={2022}, month={May}, pages={8296–8305} }
 @article{dara_mast_razgoniaev_hauke_castellano_ostrowski_2022, title={Real-Time and In Situ Viscosity Monitoring in Industrial Adhesives Using Luminescent Cu(I) Phenanthroline Molecular Sensors}, volume={7}, ISSN={["1944-8252"]}, url={https://doi.org/10.1021/acsami.2c06554}, DOI={10.1021/acsami.2c06554}, abstractNote={Monitoring the viscosity of polymers in real-time remains a challenge, especially in confined environments where traditional rheological measurements are hard to apply. In this study, we have utilized the luminescent complex [Cu(diptmp)2]+ (diptmp = 2,9-diisopropyl-3,4,7,8-tetramethyl-1,10-phenanthroline) as an optical probe for real-time sensing of viscosity in various adhesives during the curing process (viscosity increases). The emission lifetime of the triplet metal-to-ligand charge transfer (3MLCT) state of [Cu(diptmp)2]+ in epoxy adhesive increased exponentially during curing, similar to viscosity values obtained from oscillatory rheology. The longer lifetime in higher viscosity materials was attributed to changes in the excited-state deactivation processes from a known Jahn-Teller distortion in the Cu(I) geometry from tetrahedral in the ground state to square planar in the excited state. The real-time viscosity was also monitored reversibly by emission lifetime during polymer swelling (viscosity and lifetime decrease) and unswelling (viscosity and lifetime increase). Monitoring emission lifetime, unlike measuring the excited-state lifetime via transient absorption measurements in our previous study, allowed us to measure viscosity in opaque samples which scatter light. The optical probe [Cu(diptmp)2]+ in Gorilla Glue adhesive showed a clear correlation of the emission intensity or lifetime to viscosity during the curing process. We have also compared these lifetime changes using [Ru(bpy)3]2+ (bpy = bipyridine) as a control. [Cu(diptmp)2]+ showed not only a higher emission lifetime but also more ubiquity as a real-time viscosity sensor.}, journal={ACS APPLIED MATERIALS & INTERFACES}, author={Dara, Ankit and Mast, Derek M. and Razgoniaev, Anton O. and Hauke, Cory E. and Castellano, Felix N. and Ostrowski, Alexis D.}, year={2022}, month={Jul} }
 @article{antami_bateni_ramezani_hauke_castellano_abolhasani_2021, title={CsPbI3 Nanocrystals Go with the Flow: From Formation Mechanism to Continuous Nanomanufacturing}, volume={11}, ISSN={["1616-3028"]}, url={https://doi.org/10.1002/adfm.202108687}, DOI={10.1002/adfm.202108687}, abstractNote={Abstract}, journal={ADVANCED FUNCTIONAL MATERIALS}, author={Antami, Kameel and Bateni, Fazel and Ramezani, Mahdi and Hauke, Cory E. and Castellano, Felix N. and Abolhasani, Milad}, year={2021}, month={Nov} }
 @article{rosko_wells_hauke_castellano_2021, title={Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents}, volume={60}, ISSN={["1520-510X"]}, url={https://doi.org/10.1021/acs.inorgchem.1c01242}, DOI={10.1021/acs.inorgchem.1c01242}, abstractNote={A new long-lived, visible-light-absorbing homoleptic Cu(I) metal-to-ligand charge transfer (MLCT) photosensitizer, [Cu(dchtmp)2]PF6 (dchtmp = 2,9-dicyclohexyl-3,4,7,8-tetramethyl-1,10-phenanthroline), has been synthesized, structurally characterized, and evaluated in terms of its molecular photophysics, electrochemistry, and electronic structure. Static and time-resolved transient absorption (TA) and photoluminescence (PL) spectroscopy measured on the title compound in CH2Cl2 (τ = 2.6 μs, ΦPL = 5.5%), CH3CN (τ = 1.5 μs, ΦPL = 2.6%), and THF (τ = 2.0 μs, ΦPL = 3.7%) yielded impressive photophysical metrics even when dissolved in Lewis basic solvents. The combined static spectroscopic data along with ultrafast TA experiments revealed that the pseudo-Jahn-Teller distortion and intersystem crossing dynamics in the MLCT excited state displayed characteristics of being sterically arrested throughout its evolution. Electrochemical and static PL data illustrate that [Cu(dchtmp)2]PF6 is a potent photoreductant (-1.77 V vs Fc+/0 in CH3CN) equal to or greater than all previously investigated homoleptic Cu(I) diimine complexes. Although we successfully prepared the cyclopentyl analog dcptmp (2,9-dicyclopentyl-3,4,7,8-tetramethyl-1,10-phenanthroline) using the same C-C radical coupling photochemistry as dchtmp, the corresponding Cu(I) complex could not be isolated due to the steric hindrance presented at the metal center. Ultimately, the successful preparation of [Cu(dchtmp)2]+ represents a major step forward for the design and discovery of novel earth-abundant photosensitizers made possible through a newly conceived ligand synthetic strategy.}, number={12}, journal={INORGANIC CHEMISTRY}, publisher={American Chemical Society (ACS)}, author={Rosko, Michael C. and Wells, Kaylee A. and Hauke, Cory E. and Castellano, Felix N.}, year={2021}, month={Jun}, pages={8394–8403} }
 @article{fayad_engl_danilov_hauke_reiser_castellano_2020, title={Correction to “Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)”}, volume={11}, url={https://doi.org/10.1021/acs.jpclett.0c02010}, DOI={10.1021/acs.jpclett.0c02010}, abstractNote={ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to "Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)"Remi FayadRemi FayadMore by Remi Fayad, Sebastian EnglSebastian EnglMore by Sebastian Engl, Evgeny O. DanilovEvgeny O. DanilovMore by Evgeny O. Danilovhttp://orcid.org/0000-0002-5551-3749, Cory E. HaukeCory E. HaukeMore by Cory E. Haukehttp://orcid.org/0000-0001-8822-0961, Oliver Reiser*Oliver ReiserMore by Oliver Reiserhttp://orcid.org/0000-0003-1430-573X, and Felix N. Castellano*Felix N. CastellanoMore by Felix N. Castellanohttp://orcid.org/0000-0001-7546-8618Cite this: J. Phys. Chem. Lett. 2020, 11, 14, 5749Publication Date (Web):July 7, 2020Publication History Published online7 July 2020Published inissue 16 July 2020https://pubs.acs.org/doi/10.1021/acs.jpclett.0c02010https://doi.org/10.1021/acs.jpclett.0c02010correctionACS PublicationsCopyright © 2020 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1112Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (442 KB) Get e-Alertsclose Get e-Alerts}, number={14}, journal={The Journal of Physical Chemistry Letters}, publisher={American Chemical Society (ACS)}, author={Fayad, Remi and Engl, Sebastian and Danilov, Evgeny O. and Hauke, Cory E. and Reiser, Oliver and Castellano, Felix N.}, year={2020}, month={Jul}, pages={5749–5749} }
 @article{fayad_engl_danilov_hauke_reiser_castellano_2020, title={Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)}, volume={11}, ISSN={1948-7185 1948-7185}, url={http://dx.doi.org/10.1021/acs.jpclett.0c01601}, DOI={10.1021/acs.jpclett.0c01601}, abstractNote={Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes, paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In the current study, the photochemical processes underpinning the catalytic activity of [Cu(dmp)2Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were investigated. The combined results from static spectroscopic investigations and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance (EPR) spin trapping experiments, strongly support blue light (ex = 427 or 470 nm) induced Cu-Cl homolytic bond cleavage in [Cu(dmp)2Cl]+ occurring in less than 100 femtoseconds. Based on electronic structure calculations, this bond breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer (LMCT) transition, unmasking a Cu(I) species [Cu(dmp)2]+ and a Cl• atom, thereby serving as a departure point for both Cu(I)- or Cu(II)-based photoredox transformations. No net photochemistry was observed through direct excitation of the ligand-field transitions in the red (ex = 785 or 800 nm), and all combined experiments indicated no evidence of Cu-Cl bond cleavage under these conditions. The underlying visible light-induced homolysis (VLIH) of a metal-ligand bond yielding a one electron reduced photosensitizer and a radical species, may form the basis for novel photoredox transformations based on first row transition metal complexes.}, number={13}, journal={The Journal of Physical Chemistry Letters}, publisher={American Chemical Society (ACS)}, author={Fayad, Remi and Engl, Sebastian and Danilov, Evgeny O. and Hauke, Cory E. and Reiser, Oliver and Castellano, Felix N.}, year={2020}, month={Jun}, pages={5345–5349} }
 @article{favale_hauke_danilov_yarnell_castellano_2020, title={Ligand-triplet migration in iridium(iii) cyclometalates featuring π-conjugated isocyanide ligands}, volume={49}, ISSN={1477-9226 1477-9234}, url={http://dx.doi.org/10.1039/D0DT02100H}, DOI={10.1039/d0dt02100h}, abstractNote={The degree of ancillary ligand conjugation determines Ir(iii) polychromophoric photophysical properties via manipulation of the triplet excited state manifolds.}, number={29}, journal={Dalton Transactions}, publisher={Royal Society of Chemistry (RSC)}, author={Favale, Joseph M. and Hauke, Cory E. and Danilov, Evgeny O. and Yarnell, James E. and Castellano, Felix N.}, year={2020}, pages={9995–10002} }
 @article{zhou_hauke_song_li_stang_cook_2019, title={Understanding the Effects of Coordination and Self-Assembly on an Emissive Phenothiazine}, volume={141}, url={https://doi.org/10.1021/jacs.9b00363}, DOI={10.1021/jacs.9b00363}, abstractNote={The local environment surrounding luminophores can significantly influence their photophysical properties. Herein, we report the self-assembly of a highly emissive platinum(II)-based metallacage. In order to accommodate the connectivity of the platinum(II) building block used in the self-assembly process, the luminophore-containing building block adopts a highly twisted geometry relative to its free form, leading to the emergence of an emissive transition with a radiative rate constant an order of magnitude higher than that of the free luminophore. This increased rate constant is the primary driver for the 10-fold increase in quantum yield from 4.2% to 40%. Model complexes with platinum or methyl groups bound to the nitrogen were synthesized. These complexes had lower quantum yields (10% and non-emissive, respectively) due mainly to decreases in radiative rate constants. Computational studies were conducted and indicated that the excited state of the ensembles, as well as the model complexes, is a result of charge transfer to the pyridyl groups, in contrast to the free luminophore, which involves the diphenyl sulfone moiety. The differences in quantum yields can be explained by a twist in the chromophore upon coordination of platinum or methylation on the pyridyl group, leading to intersystem crossing to a triplet state. This state then becomes more emissive with the addition of platinum, which increases the radiative rate constant via the heavy atom effect. The formation of a metallacage also decreases the non-radiative rate constant by inhibiting the intramolecular motions of the incorporated luminophore.}, number={8}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Zhou, Zhixuan and Hauke, Cory E. and Song, Bo and Li, Xiaopeng and Stang, Peter J. and Cook, Timothy R.}, year={2019}, month={Feb}, pages={3717–3722} }
 @article{hauke_oldacre_fulong_friedman_cook_2018, title={Coordination-Driven Self-Assembly of Ruthenium Polypyridyl Nodes Resulting in Emergent Photophysical and Electrochemical Properties}, volume={57}, url={https://doi.org/10.1021/acs.inorgchem.7b02657}, DOI={10.1021/acs.inorgchem.7b02657}, abstractNote={Ruthenium polypyridyl complexes are among the most studied molecular species for photochemical applications such as light-harvesting and photocatalysis, with [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) serving as an iconic example. We report the use of the [Ru(bpy)2]2+ fragment as a 90° acceptor tecton (M) in coordination-driven self-assembly to synthesize a M4L4 metallacycle (L = 4,4'-bipyridine) and a M6L4 truncated tetrahedral cage [L = 2,4,6-tris(4-pyridyl)-1,3,5-triazine]. The M6L4 cage possesses emergent properties attributed to its unique electronic structure, which results in increased visible-light absorption and an emission band that decays biexponentially with times of 3 and 790 ns. The presence of multiple ruthenium centers in the cage results in multiple RuIII/II reduction events, with a cathodic shift of the first reduction relative to that of [Ru(bpy)3]Cl2 (0.56 V vs 1.05 V). The ligand-centered reduction shifts anodically (-1.29 vs -1.64 V) versus the first bpy reduction observed in the parent [Ru(bpy)3]Cl2. The photophysical properties are explained by the existence of two localized charge-transfer states in the cage molecule: one that draws upon the bipyridine π* orbitals and the other upon the 2,4,6-tris(4-pyridyl)-1,3,5-triazine π* orbitals.}, number={7}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Hauke, Cory E. and Oldacre, Amanda N. and Fulong, Cressa Ria P. and Friedman, Alan E. and Cook, Timothy R.}, year={2018}, month={Apr}, pages={3587–3595} }
 @article{zhang_crawley_hauke_friedman_janik_cook_2017, title={A Bis(dipyrrinato) Motif as a Building Block for Polynuclear Rhenium(I) Architectures}, volume={2017}, url={https://doi.org/10.1002/ejic.201700771}, DOI={10.1002/ejic.201700771}, abstractNote={The coordination of a bis(dipyrrin) ligand (LH2) to Re(CO)5Cl delivers a dirhenium salt that serves as a precursor to a dinuclear phosphine compound or as a component of a metallacycle when combined with 4,4′‐bipyridine (bpy) to furnish a tetranuclear [{(CO)3Re}4L2(bpy)2] complex. The distorted nature of the metallacycle was determined by single‐crystal X‐ray diffraction revealing that the Re‐bpy‐Re edges are twisted by approximately 119° and the Re‐L‐Re edges are twisted by approximately 88° from the idealized rectangular plane. The ReI metallacycle exhibits luminescence (λfluo. = 592 nm; λphos. = 731 nm) in CH2Cl2 at 77 K.}, number={34}, journal={European Journal of Inorganic Chemistry}, publisher={Wiley}, author={Zhang, Yuzhen and Crawley, Matthew R. and Hauke, Cory E. and Friedman, Alan E. and Janik, Thomas S. and Cook, Timothy R.}, year={2017}, month={Sep}, pages={4055–4060} }
 @article{zhang_hauke_crawley_schurr_fulong_cook_2017, title={Increasing phosphorescent quantum yields and lifetimes of platinum-alkynyl complexes with extended conjugation}, volume={46}, url={https://doi.org/10.1039/C7DT01817G}, DOI={10.1039/C7DT01817G}, abstractNote={Designing platinum-alkynyl complexes to access a metallo-cumulene resonance form increases the quantum yield via increased rigidity.}, number={30}, journal={Dalton Transactions}, publisher={Royal Society of Chemistry (RSC)}, author={Zhang, Yuzhen and Hauke, Cory E. and Crawley, Matthew R. and Schurr, Bradley E. and Fulong, Cressa Ria P. and Cook, Timothy R.}, year={2017}, pages={9794–9800} }
 @article{zhang_crawley_hauke_friedman_cook_2017, title={Phosphorescent Decanuclear Bimetallic Pt6M4 (M = Zn, Fe) Tetrahedral Cages}, volume={56}, DOI={10.1021/acs.inorgchem.7b00501}, abstractNote={Coordination-driven self-assembly delivers discrete, nanoscopic architectures that may preserve or enhance the physicochemical properties of their parent building blocks. Herein, we report the syntheses, characterization, and photophysical properties of two tetrahedral cages, [ZnII4L6](PF6)8 (C1) and [FeII4L6](OTf)8 (C2), where L = PtII(PEt3)2(C≡C-bpy)2 (PEt3 = triethylphosphine; C≡C-bpy = 5-ethynyl-2,2'-bipyridine) and OTf = trifluoromethanesulfonate. C1 and C2 were assembled in isolated yields of 72% and 81% by treating 2 equiv of Zn(NO3)2·6H2O or Fe(OTf)2 with 3 equiv of L, respectively. Both cages were fully characterized by NMR, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction (SCXRD). The local D3 symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and ΛΛΛΛ) are formed based on 1H NMR and SCXRD. C1 exhibits phosphorescence centered at 545 nm with a quantum yield of 10% in N2-degassed acetonitrile at 25 °C. The quantum yield of C2 is significantly lower due to a nonradiative relaxation from 5MC (MC = metal-centered) states introduced by the FeII nodes.}, number={8}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Zhang, Yuzhen and Crawley, Matthew R. and Hauke, Cory E. and Friedman, Alan E. and Cook, Timothy R.}, year={2017}, month={Apr}, pages={4258–4262} }
 @article{zhang_fulong_hauke_crawley_friedman_cook_2017, title={Photophysical Enhancement of Triplet Emitters by Coordination-Driven Self-Assembly}, volume={23}, DOI={10.1002/chem.201700614}, abstractNote={Abstract}, number={19}, journal={Chemistry - A European Journal}, publisher={Wiley-Blackwell}, author={Zhang, Yuzhen and Fulong, Cressa Ria P. and Hauke, Cory E. and Crawley, Matthew R. and Friedman, Alan E. and Cook, Timothy R.}, year={2017}, month={Mar}, pages={4532–4536} }
 @article{yan_wang_hauke_cook_wang_saha_zhou_zhang_li_huang_et al._2015, title={A Suite of Tetraphenylethylene-Based Discrete Organoplatinum(II) Metallacycles: Controllable Structure and Stoichiometry, Aggregation-Induced Emission, and Nitroaromatics Sensing}, volume={137}, DOI={10.1021/jacs.5b10130}, abstractNote={Materials that organize multiple functionally active sites, especially those with aggregation-induced emission (AIE) properties, are of growing interest due to their widespread applications. Despite promising early architectures, the fabrication and preparation of multiple AIEgens, such as multiple tetraphenylethylene (multi-TPE) units, in a single entity remain a big challenge due to the tedious covalent synthetic procedures often accompanying such preparations. Coordination-driven self-assembly is an alternative synthetic methodology with the potential to deliver multi-TPE architectures with light-emitting characteristics. Herein, we report the preparation of a new family of discrete multi-TPE metallacycles in which two pendant phenyl rings of the TPE units remain unused as a structural element, representing novel AIE-active metal-organic materials based on supramolecular coordination complex platforms. These metallacycles possess relatively high molar absorption coefficients but weak fluorescent emission under dilute conditions because of the ability of the untethered phenyl rings to undergo torsional motion as a non-radiative decay pathway. Upon molecular aggregation, the multi-TPE metallacycles show AIE-activity with markedly enhanced quantum yields. Moreover, on account of their AIE characteristics in the condensed state and ability to interact with electron-deficient substrates, the photophysics of these metallacycles is sensitive to the presence of nitroaromatics, motivating their use as sensors. This work represents a unification of themes including molecular self-assembly, AIE, and fluorescence sensing and establishes structure-property-application relationships of multi-TPE scaffolds. The fundamental knowledge obtained from the current research facilitates progress in the field of metal-organic materials, metal-coordination-induced emission, and fluorescent sensing.}, number={48}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Yan, Xuzhou and Wang, Haoze and Hauke, Cory E. and Cook, Timothy R. and Wang, Ming and Saha, Manik Lal and Zhou, Zhixuan and Zhang, Mingming and Li, Xiaopeng and Huang, Feihe and et al.}, year={2015}, pages={15276–15286} }