Dual action agents containing a cysteine protease inhibitor and Ru-based photosensitizer for photodynamic therapy (PDT) were designed, synthesized, validated in 2D culture 3D functional imaging assays of triple-negative human breast cancer (TNBC). These combination deliver release PDT to tumor cells cause cell death upon irradiation with visible light, while at the same time inactivating cathespin B (CTSB), strongly associated invasive metastatic behavior. In total five complexes synthesized...

A series of Ru(ii) complexes bearing the tridentate 2,6-di(quinolin-2-yl)pyridine (dqpy) ligand were designed to undergo photoinduced dissociation with red/near-IR light. The [Ru(dqpy)(L)(CH

We report the synthesis and photochemical biological characterization of first selective potent metal-based inhibitors cytochrome P450 3A4 (CYP3A4), major human drug metabolizing enzyme. Five Ru(II)-based derivatives were prepared from two analogs CYP3A4 inhibitor ritonavir, 4 6: [Ru(tpy)(L)(6)]Cl2 (tpy = 2,2':6',2″-terpyridine) with L 6,6'-dimethyl-2,2'-bipyridine (Me2bpy; 8), dimethylbenzo[i]dipyrido[3,2-a:2',3'-c]phenazine (Me2dppn; 10)...

A new complex, [Ru(tpy)(dppn)(Cbz-Leu-NHCH2CN)]2+ (1, tpy = 2,2':6',2''-terpyridine, dppn benzo[i]dipyrido[3,2-a:2',3'-c]phenazine) was synthesized and its photochemical properties were investigated. This complex undergoes photorelease of the Cbz-Leu-NHCH2CN ligand, a known cathepsin K inhibitor, with quantum yield, Φ450, 0.0012(4) in water (λirr 450 nm). In addition, 1 sensitizes production singlet oxygen upon visible light irradiation ΦΔ, 0.64(3) CH3OH. The photophysical compared those...

A series of 12 Ru(II) complexes the type [Ru(tpy)(L)(CH3CN)]n+, 1–12, containing tridentate tpy ligand (tpy = 2,2′:6′,2″-terpyridine) and various bidentate ancillary ligands, L, were synthesized evaluated for their ability to photodissociate CH3CN, a model nitrile-containing drugs. Although ligands chosen display similar degree steric bulk around metal center in ground state, photosubstitution efficiencies 1–12 vary by approximately an order magnitude. The most electron-donating 8–11,...

Ru(ii)-polypyridyl cages with sterically bulky bidentate ligands provide efficient photochemical release of the anticancer drug imatinib using low energy visible light, imparting spatiotemporal control over bioavailability. The light-activated is maintained when Ru(ii) cage covalently coupled to an antibody, which expected localize selectively on tumor.

Four metalo-intercalators ([Ru₃(μ₃-O)(μ₂-OAc)₅(L)(py)₂]PF₆, L = phenazines) present high DNA intercalation constants and HSA affinity. They are active against melanoma cancer <italic>T. Cruzi</italic> parasite.

The synthesis, chemical and biological characterization of seven Ru(II) polypyridyl complexes containing acetylacetonate (acac) ligands are reported. Electronic absorption spectra were determined electrochemical potentials consistent with Ru(III/II) couples ranging from +0.60 to +0.73 V vs Ag/AgCl measured. A series screened against MDA-MB-231, DU-145, MCF-10A cell lines evaluate their cytotoxicities in cancer normal lines. Although most either nontoxic or equipotent cells lines, compound 1,...

Nonlinear optical (NLO) materials are able to modulate responses of electromagnetic radiation, leading phenomena critical modern telecommunications technologies. The last two decades have seen significant advances in the area molecular nonlinear chromophores, particularly with respect reverse-saturable absorption (RSA). Here, we introduce a strategy for intense excited-state (ESA) that involves bis-cyclometalated iridium complexes isocyanide ancillary ligands decorated pyrene triplet...

In this work, we introduce a series of cyclometalated iridium complexes and evaluate the suitability class compounds in nonlinear optical (NLO) applications, with an emphasis on long-lived, panchromatic reverse-saturable absorption (RSA). The investigated are represented by general formula [Ir(C^N)2(CNArdmp)2]+, (C^N = cyclometalating ligand, CNArdmp 2,6-dimethylphenyl isocyanide). Seven such were synthesized characterized, including in-depth analysis their photophysical properties (UV-vis...

Despite 40 years of interest in chalcogenopyrylium polymethine dyes, significant gaps remain our understanding their photophysical properties. These hinder efforts to apply such dyes as photodynamic therapy and/or biomedical sensing agents where a complete excited-state dynamics and chemistry are important. For example, despite previous reports that establish singlet oxygen yields high 12% for certain we observe no evidence 1O2 from direct phosphorescence measurements. We now fill many these...

Transition metal complexes are utilized in a broad array of applications such as photoredox catalysis, photodynamic therapy, biological sensing, and phosphors for organic light-emitting diodes. Furthermore, many transition metals demonstrate two photon absorption reverse saturable (RSA) characteristics increasing their non-linear optical materials. Iridium is particular interest to our work because its strong spin-orbit coupling, which allows multiple excited states, thereby the compound's...

Transition metal chromophores (TMCs) are a widely studied class of materials due to their synthetic tunability and photophysical properties. Second- third-row d⁶ TMCs, such as Ru^II or Ir^III, particular importance large spin-orbit coupling constants the prevalence metal-to-ligand charge transfer (MLCT) excited states. TMCs have found broad application in organic light-emitting diodes (OLEDs), photoredox catalysis, photodynamic therapy, non-linear optics (NLO)....

Recently, cyclometalated iridium (III) complexes have been studied for use as non-linear optical (NLO) materials. Reports of both two photon absorption (2PA) and reverse saturable (RSA) properties warrant their continued development enhanced performance. Cyclometalating ligands used with commonly ligate through an anionic carbon on a phenyl ring nitrogen adjacent ring, such 2- phenylpyridine (ppy), 1-phenylpyrazole (ppz), 2-phenylbenzoxazole (pbo), derivatives. These contain rotational...

Cyclometalated iridium complexes have long been prominent in electroluminescent applications, and several recent studies shown that this family of compounds offers potential advantages for designing materials with reversesaturable absorption (RSA) other nonlinear optical properties. In talk we present a comprehensive study the excited-state properties three bis-cyclometalated general formula [Ir(C^N)₂(CN^dmp)₂]⁺, where C^N is variable...

Our group has developed cyclometalated iridium complexes as nonlinear optical materials, focusing especially on reversesaturable absorption (RSA). Cationic with isocyanide ancillary ligands offer several advantages in this context, elaborated previous studies. This talk describes next-generation of the general formula [Ir(C^N)₂(CNAr)₂]⁺, where C^N is a variable cyclometalating ligand and CNAr pyrene-decorated aryl isocyanide. In these compounds dominant...

Cyclometalated iridium complexes are a specific class of transition metal chromophores (TMCs) widely employed as phosphors in organic light emitting diodes (OLEDs), photoredox catalysts, and increasingly non-linear optical (NLO) materials. This research investigated the effect derivatization on parent complex [Ir(pbt)2(acac)], where pbt is 2-phenylbenzothiazole acac acetylacetonate. Specifically, hole transport groups, either triphenylamines or carbazoles, were installed at different...