Direct O2 mediated oxidation of a Ni(II)N3O structural model complex for the active site of nickel acireductone dioxygenase (Ni-ARD): characterization, biomimetic reactivity, and enzymatic implications.

A new biomimetic model complex of the active site of acireductone dioxygenase (ARD) was synthesized and crystallographically characterized ([Ni(ii)(N-(ethyl-N'Me2)(Py)(2-t-ButPhOH))(OTf)]-1). 1 displays carbon-carbon oxidative cleavage activity in the presence of O2 towards the substrate 2-hydroxyacetophenone. This reactivity was monitored via UV-Visible and NMR spectroscopy. We postulate that the reactivity of 1 with O2 leads to the formation of a putative Ni(III)-superoxo transient species resulting from the direct activation of O2via the nickel center during the oxidative reaction. This proposed intermediate and reaction mechanism were studied in detail using DFT calculations. 1 and its substrate bound derivatives display reactivity toward mild outer sphere oxidants, suggesting ease of access to high valent Ni coordination complexes, consistent with our calculations. If confirmed, the direct activation of O2 at a nickel center could have implications for the mechanism of action of ARD and other nickel-based dioxygenases and their respective non-traditional, enzymatic moonlighting functions, as well as contribute to a general understanding of direct oxidation of nickel(II) coordination complexes by O2.

Cu-Catalyzed Three-Component Alkene Carboamination: Mechanistic Insights and Rational Design to Overcome Limitations.

Herein, we report mechanistic investigations into the Cu-catalyzed three-component carboamination of alkenes with α-halo carbonyls and aryl amines via an oxocarbenium intermediate. Monitoring the reaction reveals the formation of transient atom transfer radical addition (ATRA) intermediates with both electron-neutral and deficient vinyl arenes as well as unactivated alkenes. Based on our experimental studies and density functional theory calculations, the oxocarbenium is generated through atom transfer and subsequent intramolecular substitution. Further, mechanistic factors that dictate the regioselectivity of the nucleophilic attack onto the oxocarbenium to afford the γ-amino ester, γ-iminolactone, or γ-lactone are discussed. A strategy to overcome scope limitation with respect to unactivated alkenes is developed using the mechanistic insights gained herein. Finally, we demonstrate that under modified conditions, our Cu catalyst enables the ATRA reaction between a variety of alkyl halides and vinyl arenes/α-olefins, and we present a one-pot, two-step carbofunctionalization with an array of nucleophiles through ATRA/SN2.

Multi-phosphine-chelated iron-carbide clusters via redox-promoted ligand exchange on an inert hexa-iron-carbide carbonyl cluster, [Fe6(µ6-C)(µ2-CO)4(CO)12]2.

We report the reactivity, structures and spectroscopic characterization of reactions of phosphine-based ligands (mono-, di- and tri-dentate) with iron-carbide carbonyl clusters. Historically, the archetype of this cluster class, namely [Fe6(µ6-C)(µ2-CO)4(CO)12]2-, can be prepared on a gram-scale but is resistant to simple ligand substitution reactions. This limitation has precluded the relevance of iron-carbide clusters relating to organometallics, catalysis and the nitrogenase active site cluster. Herein, we aimed to derive a simple and reliable method to accomplish CO → L (where L = phosphine or other general ligands) substitution reactions without harsh reagents or multi-step synthetic strategies. Ultimately, our goal was ligand-based chelation of an Fe n (µ n -C) core to achieve more synthetic control over multi-iron-carbide motifs relevant to the nitrogenase active site. We report that the key intermediate is the PSEPT-non-conforming cluster [Fe6(µ6-C)(CO)16] (2: 84 electrons), which can be generated in situ by the outer-sphere oxidation of [Fe6(µ6-C)(CO)16]2- (1: closo, 86 electrons) with 2 equiv. of [Fc]PF6. The reaction of 2 with excess PPh3 generates a singly substituted neutral cluster [Fe5(µ5-C)(CO)14PPh3] (4), similar to the reported reactivity of the substitutionally active cluster [Fe5(µ5-C)(CO)15] with monodentate phosphines (Cooke & Mays, 1990). In contrast, the reaction of 2 with flexible, bidentate phosphines (DPPE and DPPP) generates a wide range of unisolable products. However, the rigid bidentate phosphine bis(diphenylphosphino)benzene (bdpb) disproportionates the cluster into non-ligated Fe3-carbide anions paired with a bdpb-supported Fe(ii) cation, which co-crystallize in [Fe3(µ3-CH)(µ3-CO)(CO)9]2[Fe(MeCN)2(bdpb)2] (6). A successful reaction of 2 with the tripodal ligand Triphos generates the first multi-iron-chelated, authentic carbide cluster of the formula [Fe4(µ4-C)(κ3-Triphos)(CO)10] (9). DFT analysis of the key (oxidized) intermediate 2 suggests that its (µ6-C)Fe6 framework remains fully intact but is distorted into an axially compressed, 'ruffled' octahedron distinct from the parent closo cluster 1. Oxidation of the cluster in non-coordinating solvent allows for the isolation and crystallization of the CO-saturated, intact closo-analogue [Fe6(µ6-C)(CO)17] (3), indicating that the intact (µ6-C)Fe6 motif is retained during initial oxidation with [Fc]PF6. Overall, we demonstrate that redox modulation beneficially 'bends' Wade-Mingo's rules via the generation of electron-starved (non-PSEPT) intermediates, which are the key intermediates in promoting facile CO → L substitution reactions in iron-carbide-carbonyl clusters.

A Method for Rigorously Selective Capture and Simultaneous Fluorescent Labeling of N-Terminal Glycine Peptides.

Although chemical methods for the selective derivatization of amino acid (AA) side chains in peptides and proteins are available, selective N-terminal labeling is challenging, especially for glycine, which has no side chain at the α-carbon position. We report here a double activation at glycine's α-methylene group that allows this AA to be differentiated from the other 19 AAs. A condensation reaction of dibenzoylmethane with glycine results in the formation of an imine, and subsequent tautomerization is followed by intramolecular cyclization, leading to the formation of a fluorescent pyrrole ring. Additionally, the approach exhibits compatibility with AAs possessing reactive side chains. Further, the method allows for selective pull-down assays of N-terminal glycine peptides from mixtures without prior knowledge of the N-terminal peptide distribution.

A Janus carbaporphyrin pseudo-dimer.

Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented. It displays antiaromatic characteristics on the fused side and nonaromatic behavior on the unfused side. A newly synthesized tetraphenylene (TPE) linked bis-dibenzihomoporphyrin 8 and a previously reported dibenzo[g,p]chrysene (DBC) linked bis-dicarbacorrole 9 were prepared as controls. Comprehensive analyses, including 1H NMR spectral studies, single crystal X-ray diffraction analyses, and DFT calculations, validate the mixed character of 5. A further feature of the Janus pseudo-dimer 5 is that it may be transformed into a heterometallic complex, with one side coordinating a Cu(III) center and the other stabilizing a BODIPY complex. This disparate regiochemical reactivity underscores the potential of carbaporphyrin dimers as versatile frameworks, with electronic features and site-specific coordination chemistry controlled through asymmetry. These findings position carbaporphyrin dimers as promising candidates for advances in electronic structure studies, coordination chemistry, materials science, and beyond.

Cyclopentadienyl capped thorium(IV) porphyrinoid complex.

The reaction between Th(IV) dipyriamethyrin dichloride and sodium cyclopentadienyl (Cp) results in the formation of a cyclopentadienyl capped thorium dipyriamethyrin complex, which to our knowledge represents the first expanded porphyrin f-element Cp complex.

Nanographene-Fused Expanded Carbaporphyrin Tweezers.

A nanographene-fused expanded carbaporphyrin (5) and its BF2 complex (6) were synthesized. Single-crystal X-ray structures revealed that 5 and 6 are connected by two hexa-peri-hexabenzocoronene (HBC) units and two dipyrromethene or BODIPY units, respectively. As prepared, 5 and 6 both show nonaromatic character with figure-of-eight carbaoctaphyrin (1.1.1.0.1.1.1.0) cores and adopt tweezers-like conformations characterized by a partially confined space between the two constituent HBC units. The distance between the HBC centers is >10 Å, while the dihedral angles between the two HBC planes are 30.5 and 35.2° for 5 and 6, respectively. The interactions between 5 and 6 and fullerene C60 were studied both in organic media and in the solid state. Proton NMR spectral titrations of 5 and 6 with C60 revealed a 1:1 binding mode for both macrocycles. In toluene-d8, the corresponding binding constants were determined to be 1141 ± 17 and 994 ± 10 M-1 for 5 and 6, respectively. Single-crystal X-ray diffraction structural analyses confirmed the formation of 1:1 fullerene inclusion complexes in the solid state. The C60 guests in both complexes are found within triangular pockets composed of two HBC units from the tweezers-like receptor most closely associated with the bound fullerene, as well as an HBC unit from an adjacent host. Femtosecond transient absorption measurements revealed subpicosecond ultrafast charge separation between 5 (and 6) and C60 in the complexes. To the best of our knowledge, the present report provides the first example wherein a nanographene building block is incorporated into the core of a porphyrinic framework.

Photochemical charge accumulation in a heteroleptic copper(i)-anthraquinone molecular dyad via proton-coupled electron transfer.

Developing efficient photocatalysts that perform multi electron redox reactions is critical to achieving solar energy conversion. One can reach this goal by developing systems which mimic natural photosynthesis and exploit strategies such as proton-coupled electron transfer (PCET) to achieve photochemical charge accumulation. We report herein a heteroleptic Cu(i)bis(phenanthroline) complex, Cu-AnQ, featuring a fused phenazine-anthraquinone moiety that photochemically accumulates two electrons in the anthraquinone unit via PCET. Full spectroscopic and electrochemical analyses allowed us to identify the reduced species and revealed that up to three electrons can be accumulated in the phenazine-anthraquinone ring system under electrochemical conditions. Continuous photolysis of Cu-AnQ in the presence of sacrificial electron donor produced doubly reduced monoprotonated photoproduct confirmed unambiguously by X-ray crystallography. Formation of this photoproduct indicates that a PCET process occurred during illumination and two electrons were accumulated in the system. The role of the heteroleptic Cu(i)bis(phenanthroline) moiety participating in the photochemical charge accumulation as a light absorber was evidenced by comparing the photolysis of Cu-AnQ and the free AnQ ligand with less reductive triethylamine as a sacrificial electron donor, in which photogenerated doubly reduced species was observed with Cu-AnQ, but not with the free ligand. The thermodynamic properties of Cu-AnQ were examined by DFT which mapped the probable reaction pathway for photochemical charge accumulation and the capacity for solar energy stored in the process. This study presents a unique system built on earth-abundant transition metal complex to store electrons, and tune the storage of solar energy by the degree of protonation of the electron acceptor.

Deferasirox Derivatives: Ligands for the Lanthanide Series.

Deferasirox is an FDA-approved iron chelator used in the treatment of iron toxicity. In this work, we report the use of several deferasirox derivatives as lanthanide chelators. Solid-state structural studies of three representative trivalent lanthanide cations, La(III), Eu(III), and Lu(III), revealed the formation of 2:2 complexes in the solid state. A 1:1 stoichiometry dominates in DMSO solution, with Ka values of 472 ± 14, 477 ± 11, and 496 ± 15 M-1 being obtained in the case of these three cations, respectively. Under the conditions of competitive precipitation in the presence of triethylamine, high selectivity (up to 80%) for lutetium(III) was observed in competition with La(III), Ce(III), and Eu(III). Theoretical calculations provided support for the observed selective crystallization.

Diphenylpyrrole-Strapped Calix[4]pyrrole Extractant for the Fluoride and Chloride Anions.

The anion binding features of diphenylpyrrole-strapped calix[4]pyrrole 1 have been investigated by means of 1 H NMR spectroscopy and ITC (isothermal titration calorimetry), as well as single crystal X-ray diffraction analyses. Receptor 1 bearing an auxiliary pyrrolic NH donor and solubilizing phenyl groups on the strap was found to bind F- , Cl- , and Br- as their tetrabutylammonium salts with high affinity in DMSO-d6 . In addition, receptor 1 was found to extract the fluoride anion (as both its tetraethylammonium (TEA+ ) and tetrabutylammonium (TBA+ ) salts), as well as the chloride anion into chloroform-d from an aqueous source phase. Cation metathesis using TBAI or the use of a dual host approach involving crown ethers enabled receptor 1 to extract simple alkali metal fluoride or chloride salts from water. Quantitative binding of NaF by receptor 1 was observed in 20 % D2 O-DMSO-d6 allowing for the direct determination of the NaF concentration in an unknown sample.

Optical detection of alcohols with a Cu(I)HETPHEN complex by reversible aldehyde to hemiacetal conversion.

A heteroleptic copper(I) bis(phenanthroline) complex with aldehyde groups at the 4,7 positions of the phenanthroline ligand was synthesized. The complex is responsive to alcohol, resulting in a distinct colour change caused by the facile reaction of the aldehyde group with alcohol, forming a hemiacetal product. The aldehyde species can be regenerated after heating the intermediate at 80 °C for 10 minutes, demonstrating the reusability of the complex for alcohol detection. This work presents a new strategy for applying transition metal complexes in small molecule sensing by installing functional groups in the secondary coordination sphere which reversibly react with analytes.

Changing Directions: Influence of Ligand Electronics on the Directionality and Kinetics of Photoinduced Charge Transfer in Cu(I)Diimine Complexes.

A key challenge to the effective utilization of solar energy is to promote efficient photoinduced charge transfer, specifically avoiding unproductive, circuitous electron-transfer pathways and optimizing the kinetics of charge separation and recombination. We hypothesize that one way to address this challenge is to develop a fundamental understanding of how to initiate and control directional photoinduced charge transfer, particularly for earth-abundant first-row transition-metal coordination complexes, which typically suffer from relatively short excited-state lifetimes. Here, we report a series of functionalized heteroleptic copper(I)bis(phenanthroline) complexes, which have allowed us to investigate the directionality of intramolecular photoinduced metal-to-ligand charge transfer (MLCT) as a function of the substituent Hammett parameter. Ultrafast transient absorption suggests a complicated interplay of MLCT localization and solvent interaction with the Cu(II) center of the MLCT state. This work provides a set of design principles for directional charge transfer in earth-abundant complexes and can be used to efficiently design pathways for connecting the molecular modules to catalysts or electrodes and integration into systems for light-driven catalysis.

Multifaceted Chiral Probe 2,3-Dihydro-4-hydroxy-chromene Schiff Base in Detecting Cu2+ Ions, l-Histidine, and Indazole: Spectroscopic Investigation and Confocal and Live Cell Imaging.

2,3-Dihydro-4-hydroxy-chromene-4(N)-ethyl thiosemicarbazone (probe F4) is used as a chemosensor, and it selectively detected Cu2+ ions among the metal ions by showing fluorescence "TURN ON" behavior. The stoichiometric binding of the probe with Cu2+ (CF4) was confirmed by Job's plot and mass spectroscopy. Further, CF4 was used as a sensor for the detection of l-amino acids and N-heterocyclic compounds. Among them, CF4 selectively detected l-histidine by showing fluorescence "TURN-OFF" behavior and selectively detected indazole by showing fluorescence "TURN-ON" behavior. These behaviors were further confirmed by in vivo live cell imaging studies by using Caenorhabditis elegans as a model. In vitro cytotoxicity was assayed for probe F4, complex CF4, and CF4 with l-histidine and indazole. The IC50 concentration was used for confocal imaging studies by using the MDA-MB-231 cell line (breast cancer cell line).

Fluorescent copolymer aggregate sensor for lithium chloride.

We report a copolymeric fluorescent sensor that is selective for lithium chloride. The two constituent polymers comprise pendent triphenylethylene (TPE) moieties for aggregate induced emission (AIE) along with either strapped-calix[4]pyrrole or secondary ammonium groups that drive aggregation via self-assembly upon polymer mixing. Addition of LiCl in acetonitrile disrupts the strapped-calix[4]pyrrole/secondary ammonium chloride salt host-guest crosslinks leading to disaggregation of the polymer chains and a decrease in TPE emission. The lack of AIE perturbation upon addition of NaCl, KCl, MgCl2 or CaCl2 provides for high selectivity for LiCl relative to potential interferants. This supramolecular dual polymer approach could serve as a complement to more traditional sensor systems.

Cyclo[2]carbazole[2]pyrrole: a preorganized calix[4]pyrrole analogue.

A cyclo[2]carbazole[2]pyrrole (2) consisting of two carbazoles and two pyrroles has been synthesized by directly linking the carbazole 1- and 8-carbon atoms to the pyrrole α-carbon atoms. Macrocycle 2 is an extensively conjugated 16-membered macrocyclic ring that is fixed in a pseudo-1,3-alternate conformation. This provides a preorganized anion binding site consisting of two pyrrole subunits. 1H NMR spectroscopic analysis revealed that only the two diagonally opposed pyrrole NH protons, as opposed to the carbazole protons, take part in anion binding. Nevertheless, cyclo[2]carbazole[2]pyrrole 2 binds representative anions with higher affinity in CD2Cl2 than calix[4]pyrrole (1), a well-studied non-conjugated tetrapyrrole macrocycle that binds anions via four pyrrolic NH hydrogen bond interactions. On the basis of computational studies, the higher chloride anion affinity of receptor 2 relative to 1 is rationalized in terms of a larger binding energy and a lower host strain energy associated with anion complexation. In the presence of excess fluoride or bicarbonate anions, compound 2 loses two pyrrolic NH protons to produce a stable dianionic macrocycle [2-2H]2- displaying a quenched fluorescence.

Cyclic Carbaporphyrin Arrays.

Two cyclic carbaporphyrin arrays (trimer 6 and tetramer 7) were synthesized from a dibrominated carbaporphyrin precursor (5) via a one-pot Yamamoto-type coupling. Single-crystal X-ray diffraction analyses revealed that 6 and 7 contain three and four covalently linked carbaporphyrin (formally dicarbacorrole) units, respectively. Trimer 6 adopts a roughly planar conformation and tetramer 7 adopts an up-and-down zig-zag conformation. Both 6 and 7 contain a [n]cyclo-meta-phenylene ([n]CMP) core, namely, [6]- and [8]CMP for 6 and 7, respectively. Transient absorption (TA) anisotropy and pump-power-dependent excited-state decay studies provided evidence for excitation energy transfer (EET) within both trimer 6 and tetramer 7. The exciton energy hopping (EEH) times were estimated to be 18 and 35 ps for 6 and 7, respectively, as inferred from pump-power-dependent TA measurements. Since the center-to-center distances between adjacent carbaporphyrin units are similar in 6 and 7, the different EEH times are attributed to differences in the orientation of the transition dipoles in these two congeneric arrays. The orientation factor κ2, the key parameter defining the Förster resonance energy transfer efficiency, was calculated to be 2.15 and 1.03 for 6 and 7, respectively, a finding that supports the shorter excitation energy hopping time seen in the case of trimer 6. To our knowledge, this is the first time that covalently linked cyclic carbaporphyrin arrays were synthesized using a single carbaporphyrin as the starting point and that EET between carbaporphyrin subunits constrained within a well-defined polycyclic framework has been correlated with structural differences.

Supramolecular Recognition within a Nanosized "Buckytrap" That Exhibits Substantial Photoconductivity.

We report here a nanosized "buckytrap", 1, constructed from two bis-zinc(II) expanded-TTF (exTTF) porphyrin subunits. Two forms, 1a and 1b, differing in the axial ligands, H2O vs tetrahydrofuran (THF), were isolated and characterized. Discrete host-guest inclusion complexes are formed upon treatment with fullerenes as inferred from a single-crystal X-ray structural analyses of 1a with C70. The fullerene is found to be encapsulated within the inner pseudohexagonal cavity of 1a. In contrast, the corresponding free-base derivative (2) was found to form infinite ball-and-socket type supramolecular organic frameworks (3D-SOFs) with fullerenes, (2•C60)n or (2•C70)n. This difference is ascribed to the fact that in 1a and 1b the axial positions are blocked by a H2O or THF ligand. Emission spectroscopic studies supported a 1:1 host-guest binding stoichiometry, allowing association constants of (2.0 ± 0.5) × 104 M-1 and (4.3 ± 0.9) × 104 M-1 to be calculated for C60 and C70, respectively. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) studies of solid films of the Zn-complex 1a revealed that the intrinsic charge carrier transport, i.e., pseudo-photoconductivity (ϕ∑µ), increases upon fullerene inclusion (e.g., ϕ∑µ = 1.53 × 10-4 cm2 V-1 s-1 for C60⊂(1a)2 and ϕ∑µ = 1.45 × 10-4 cm2 V-1 s-1 for C70⊂(1a)2 vs ϕ∑µ = 2.49 × 10-5 cm2 V-1 s-1 for 1a) at 298 K. These findings provide support for the notion that controlling the nature of self-assembly supramolecular constructs formed from exTTF-porphyrin dimers through metalation or choice of fullerene can be used to regulate key functional features, including photoconductivity.

Mn-CUK-1: A Flexible MOF for SO2, H2O, and H2S Capture.

The environmentally benign metal-organic framework (MOF) CUK-1 based on 2,4-pyridine dicarboxylate has been prepared for the first time using Mn(II) as the inorganic node and water as the only solvent. Mn-CUK-1 shows reversible and efficient capture of H2O, SO2, and H2S. Compared to previously studied Co(II) and Mg(II) versions of the same MOF, Mn-CUK-1 also exhibited unique temperature-induced structural flexibility due to organic linker torsion, as detailed by variable-temperature single-crystal X-ray diffraction studies. Owing to this inherent solid-state flexibility, Mn-CUK-1 showed stepwise adsorption for polar gases, which induce structural deformations upon adsorption, while the nonpolar guest adsorbates were reversibly sorbed in a more classical manner. Notably, Mn-CUK-1 demonstrates the highest reported H2S capacity-to-surface area ratio among MOFs that are chemically stable toward this reactive acidic molecule. Moreover, Mn-CUK-1 displays exceptional structural stability in the presence of high relative humidity and corrosive gases and shows soft crystalline behavior triggered by changes in both the adsorption temperature and guest molecule identity.

Calix[4]pyrrole-Based Molecular Capsule: Dihydrogen Phosphate-Promoted 1:2 Fluoride Anion Complexation.

A molecular capsule (1) consisting of two calix[4]pyrroles connected via ethylene diamide linkers has been prepared as an anion receptor. 1H NMR spectroscopic studies carried out in CD2Cl2 revealed that receptor 1 recognizes a variety of anions with different binding modes and stoichiometries. For instance, receptor 1 binds fluoride and acetate with 1:2 receptor/anion stoichiometry and other test anions with 1:1 stoichiometry in solution when their respective tetrabutylammonium (TBA+) salts were used. In contrast, with tetraethylammnium (TEA+) salts, receptor 1 forms 1:2 complexes with chloride and bromide in addition to fluoride, overcoming expected Columbic repulsions between the anions co-bound in close proximity. Receptor 1 is also able to bind oxoanions, such as oxalate (C2O42-), dihydrogen phosphate (H2PO4-), sulfate (SO42-), and hydrogen pyrophosphate (HP2O73-), in the form of 1:1 complexes as the result of presumed cooperation between the two calix[4]pyrrole subunits. The selectivity of receptor 1 for fluoride versus dihydrogen phosphate varies depending on their relative concentrations. For instance, in the presence of less than 1.0 equiv of an equimolar mixture of fluoride and dihydrogen phosphate, receptor 1 shows high selectivity for dihydrogen phosphate. In contrast, in the presence of ≥2.0 anion equiv, receptor 1 binds fluoride preferentially, forming a 1:2 complex. Moreover, when treated with F-, the preformed 1:1 H2PO4- complex of receptor 1 is converted to the corresponding 1:2 receptor/fluoride complex with the release of the prebound dihydrogen phosphate anion. As inferred from gas-phase computations, this seemingly counterintuitive behavior is rationalized in terms of the precomplexed dihydrogen phosphate serving to reduce the reorganization energy required to bind two fluoride anions. The presence of a water molecule in addition to the bound fluoride anions may also favor the formation of the 1:2 F- complex. The present study provides a new approach for fine-tuning the binding selectivity of polytopic anion receptors.

Tuning the Solid- and Solution-State Fluorescence of the Iron-Chelator Deferasirox.

Deferasirox, an FDA-approved iron chelator, has gained increasing attention for use in anticancer and antimicrobial applications. Recent efforts by our group led to the identification of this core as an easy-to-visualize aggregation-induced emission platform, or AIEgen, that provides a therapeutic effect equivalent to deferasirox (J. Am. Chem. Soc. 2021, 143, 3, 1278-1283). However, the emission wavelength of the first-generation system overlapped with that of Syto9, a green emissive dye used to indicate live cells. Here, we report a library of deferasirox derivatives with various fluorescence emission profiles designed to overcome this limitation. We propose referring to systems that show promise as both therapeutic and optical imaging agents as "illuminoceuticals". The color differences between the derivatives were observable to the unaided eye (solid- and solution-state) and were in accord with the Commission Internationale de L'Eclairage (CIE) chromaticity diagram 1913. Each fluorescent derivative successfully imaged the respective spherical and rod shapes of methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa. They also displayed iron-dependent antibiotic activity. Three derivatives, ExNMe2 (3), ExTrisT (11), and ExDCM (13), display emission features that are sufficiently distinct so as to permit the multiplex (triplex) imaging of both MRSA and P. aeruginosa via stimulated emission depletion microscopy. The present deferasirox derivatives allowed for the construction of a multi-fluorophore sensor array. This array enabled the successful discrimination between Gram-positive/Gram-negative and drug-sensitive/drug-resistant bacteria. Antibiotic sensitivity and drug-resistant mutants from clinically isolated strains could also be identified and differentiated.