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1.
Inorg Chem ; 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-39008809

ABSTRACT

Positively charged ligands are scarce. Here, we report the synthesis of unprecedented cationic selenium-containing triazapentadiene ligand framework. The reaction between 2-pyridylselenyl reagents and NaN(CN)2 in a 2:1 ratio produces the sodium complexes featuring the cationic selenium-containing triazapentadiene (SeTAP) ligand. The sodium-to-metal transmetalation allows facile preparation of SeTAP metal complexes, as exemplified by the reactions with CuCl2, AgNO3, NaAuCl4, and FeCl3. Density functional theory calculations have been used to analyze and characterize the chalcogen bonding interactions observed in the solid state for these compounds. Moreover, antifungal properties of the SeTAP ligand and its metal complexes were screened for in vitro activity against several phytopathogenic fungi. Phoma eupyrena exhibited prominent sensitivity against the action of most of the tested compounds.

2.
Angew Chem Int Ed Engl ; : e202411347, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38967094

ABSTRACT

The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a s-hole interaction that is essentially absent in biocatalysis.  For this purpose, stibine catalysts were equipped with a biotin derivative and combined with streptavidin mutants to identify an efficient transfer hydrogenation catalyst for the reduction of a fluorogenic quinoline substrate.  Increased catalytic activity from wild-type streptavidin to the best mutants coincides with the depth of the s hole on the Sb(V) center, and the emergence of saturation kinetic behavior.  Michaelis-Menten analysis reveals transition-state recognition in the low micromolar range, more than three orders of magnitude stronger than the millimolar substrate recognition.  Carboxylates preferred by the best mutants contribute to transition-state recognition by hydrogen-bonded ion pairing and anion-π interactions with the emerging pyridinium product.  The emergence of challenging stereoselectivity in aqueous systems further emphasizes compatibility of pnictogen bonding with higher order systems catalysis.

3.
Dalton Trans ; 2024 Jul 10.
Article in English | MEDLINE | ID: mdl-38984589

ABSTRACT

With the objective of gaining insight into the modulation of the reduction potential of the Ni(II/I) couple, we have synthesized two mononuclear nickel(II) complexes, NiLen (H2Len = N,N'-bis(3-methoxysalicylidene)-1,2-diamino-2-methylpropane) and NiLpn (H2Lpn = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2,2-dimethylpropane) of two N2O4 donor ligands and recorded their cyclic voltammograms. Both the nickel complexes show reversible reduction processes for the Ni(II/I) couple in acetonitrile solution but the reduction potential of NiLpn (E1/2 = -1.883 V) is 188 mV more positive than that of NiLen (E1/2 = -2.071 V). In the presence of redox inactive metal ions (Li+, Na+, K+, Mg2+, Ca2+ and Ba2+), the reduction potentials are shifted by 49-331 mV and 99-435 mV towards positive values compared to NiLen and NiLpn, respectively. The shift increases with the decrease of the pKa of the respective aqua-complexes of the metal ion but is poorly co-linear; however, better linearity is found when the shift of the mono- and bi-positive metal ion aqua complexes is plotted separately. Spectrophotometric titrations of these two nickel complexes with the guest metal ions in acetonitrile showed a well-anchored isosbestic point in all cases, confirming the adduct formation of NiLen and NiLpn with the metal ions. Structural analysis of single crystals, [(NiLen)Li(H2O)2]·ClO4 (1), [(NiLpn)Li(H2O)]·ClO4 (2), [(NiLpn)2Na]·BF4 (3) and [(NiLpn)2Ba(H2O)(ClO4)]·ClO4 (4), also corroborates the heterometallic adduct formation. The orbital energies of the optimised heterometallic adducts from which electron transfers originated were calculated in order to explain the observed reduction process. A strong linear connection between the calculated orbital energies and the experimental E1/2 values was observed. According to MEP and 2D vector field plots, the largest shift for divalent metal ions is most likely caused by the local electric field that they impose in addition to Lewis acidity.

4.
Chem Commun (Camb) ; 2024 Jul 09.
Article in English | MEDLINE | ID: mdl-38978475

ABSTRACT

(ClImDipp)P-P(Dipp)˙ (1˙), a rare example of a neutral, mixed substituted diphosphene radical, has been prepared by reduction of (ClImDipp)PP(Dipp)[OTf] (2[OTf]) and (ClImDipp)PP(Cl)(Dipp) (3) with cobaltocene (CoCp2) (ClImDipp = 4,5-dichloro-1,3-bis(1,3-diisopropylphenyl)-imidazol-2-yl, Dipp = 2,6-diisopropylphenyl). Radical compound 1˙ readily activates white phosphorus (P4), resulting in the formation of an intriguing octaphosphane butterfly compound P8(ClImDipp)2(Dipp)2 (4).

5.
Angew Chem Int Ed Engl ; 63(29): e202405400, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38727609

ABSTRACT

The chemistry of light dipnictenes has been widely investigated in the last century with remarkable achievements especially for azobenzene derivatives. In contrast, distibenes and dibismuthenes are relatively rare and show very limited reactivity. Herein, we have designed a protocol using visible light to enhance the reactivity of heavy dipnictenes. Exploiting the distinctive π-π* transition, we have been able to isolate unique examples of dipnictene-cobalt complexes. The reactivity of the distibene complex was further exploited using red light in the presence of a diazoolefin to access an unusual four-membered bicyclo[1.1.0]butane analog, containing only a single carbon atom. These findings set the bases to a conceptually new strategy in heavy element double bonds chemistry where visible light is at the front seat of bond activation.

6.
RSC Adv ; 14(19): 13200-13208, 2024 Apr 22.
Article in English | MEDLINE | ID: mdl-38655483

ABSTRACT

A trinuclear linear mixed-valence centrosymmetric cobalt(iii)-cobalt(ii)-cobalt(iii) complex, [CoII{(µ-L)(µ-Hglu)CoIII(OH2)}2](ClO4)2·6H2O has been synthesized during tetradentate N2O2 donor 'Schiff base' ligand, H2L {N,N'-bis(salicylidene)-1,3-diaminopropane} and glutaric acid (H2glu) as anionic co-ligand. The complex has been characterized by spectroscopic measurements and its solid state structure has been determined by single crystal X-ray diffraction analysis. The supra-molecular assembly formed by the hydrogen bonding interactions in the solid state of the complex has been analysed using DFT calculations.

7.
Chem Asian J ; 19(7): e202301033, 2024 Apr 02.
Article in English | MEDLINE | ID: mdl-38501888

ABSTRACT

Kinases are enzymes that play a critical role in governing essential biological processes. Due to their pivotal involvement in cancer cell signaling, they have become key targets in the development of anti-cancer drugs. Among these drugs, those containing the 2,4-dihalophenyl moiety demonstrated significant potential. Here we show how this moiety, particularly the 2-fluoro-4-iodophenyl one, is crucial for the structural stability of the formed drug-enzyme complexes. Crystallographic analysis of reported kinase-inhibitor complex structures highlights the role of the halogen bonding that this moiety forms with specific residues of the kinase binding site. This interaction is not limited to FDA-approved MEK inhibitors, but it is also relevant for other kinase inhibitors, indicating its broad relevance in the design of this class of drugs.


Subject(s)
Antineoplastic Agents , Protein Kinase Inhibitors , Protein Kinase Inhibitors/pharmacology , Protein Kinase Inhibitors/chemistry , Halogens/chemistry , Binding Sites , Protein Binding , Antineoplastic Agents/pharmacology , MAP Kinase Kinase Kinases
8.
Chem Asian J ; 19(8): e202400081, 2024 Apr 16.
Article in English | MEDLINE | ID: mdl-38407495

ABSTRACT

As(III) S-adenosylmethionine methyltransferases, pivotal enzymes in arsenic metabolism, facilitate the methylation of arsenic up to three times. This process predominantly yields trivalent mono- and dimethylarsenite, with trimethylarsine forming in smaller amounts. While this enzyme acts as a detoxifier in microbial systems by altering As(III), in humans, it paradoxically generates more toxic and potentially carcinogenic methylated arsenic species. The strong affinity of As(III) for cysteine residues, forming As(III)-thiolate bonds, is exploited in medical treatments, notably in arsenic trioxide (Trisenox®), an FDA-approved drug for leukemia. The effectiveness of this drug is partly due to its interaction with cysteine residues, leading to the breakdown of key oncogenic fusion proteins. In this study, we extend the understanding of As(III)'s binding mechanisms, showing that, in addition to As(III)-S covalent bonds, noncovalent O⋅⋅⋅As pnictogen bonding plays a vital role. This interaction significantly contributes to the structural stability of the As(III) complexes. Our crystallographic analysis using the PDB database of As(III) S-adenosylmethionine methyltransferases, augmented by comprehensive theoretical studies including molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) analysis, emphasizes the critical role of pnictogen bonding in these systems. We also undertake a detailed evaluation of the energy characteristics of these pnictogen bonds using various theoretical models. To our knowledge, this is the first time pnictogen bonds in As(III) derivatives have been reported in biological systems, marking a significant advancement in our understanding of arsenic's molecular interactions.


Subject(s)
Methyltransferases , Methyltransferases/metabolism , Methyltransferases/chemistry , Humans , Models, Molecular , Static Electricity , Quantum Theory , S-Adenosylmethionine/chemistry , S-Adenosylmethionine/metabolism , Arsenic/chemistry , Arsenic/metabolism
9.
Molecules ; 29(3)2024 Jan 30.
Article in English | MEDLINE | ID: mdl-38338397

ABSTRACT

Zn(II) coordination polymers are being increasingly studied for their stability and properties. Similarly, there is a growing interest in imidazo[1,5-a]pyridine derivatives, which show great potential in luminescence and pharmaceutical applications. In this work, we successfully synthesized and crystallized three new coordination polymers, using Zn(II) as the metallic node, dicarboxylic acids of different length and nature as linkers, and a linear ditopic imidazo[1,5-a]pyridine derivative, to explore the role of this molecule as a propagator of the dimensionality of the structure or as an ancillary ligand. Our work demonstrates the structural capability of imidazo[1,5-a]pyridines in an unexplored domain for this family of ligands. Notably, we observed a pronounced ability of this heterocyclic scaffold to establish π···π interactions in the solid state. The supramolecular π-stacked assemblies were theoretically analyzed using DFT calculations based on model structures.

10.
Sci Rep ; 14(1): 581, 2024 01 05.
Article in English | MEDLINE | ID: mdl-38182630

ABSTRACT

Early identification of ATTRv amyloidosis disease onset is still often delayed due to the lack of validated biomarkers of this disease. Light chain neurofilament (NfL) have shown promising results in early diagnosis in this disease, but data is still needed, including with alternative measuring methods. Our aim was to study the levels of NfL measured by ELISA. Furthermore, interstitial matrix metalloproteinase type 1 (MMP-1) serum levels were measured as a potential new biomarker in ATTRv. Serum NfL and MMP-1 were measured using ELISA assays in 90 participants (29 ATTR-V30M patients, 31 asymptomatic V30M-TTR variant carriers and 30 healthy controls). Median NfL levels among ATTRv amyloidosis patients were significantly higher (116 pg/mL vs 0 pg/mL in both comparison groups). The AUC comparing ATTRv amyloidosis patients and asymptomatic carriers was 0.90 and the NfL concentration of 93.55 pg/mL yielded a sensitivity of 79% and a specificity of 87%. NfL levels had a significant positive correlation with NIS values among patients. We found a negative significant correlation between eGFR and NfL levels. Finally, MMP1 levels were not different between groups. Evidence of NfL use for early diagnosis of ATTR-PN amyloidosis is growing. ELISA seems a reliable and available technique for it quantification. Decreased GFR could influence NfL plasma levels.


Subject(s)
Amyloid Neuropathies, Familial , Matrix Metalloproteinase 1 , Humans , Amyloid Neuropathies, Familial/diagnosis , Early Diagnosis , Biomarkers
11.
Inorg Chem ; 63(1): 191-202, 2024 Jan 08.
Article in English | MEDLINE | ID: mdl-38108293

ABSTRACT

Cocrystallization of the dimeric [Cu2(µ-I)2(CNXyl)4] (Xyl = 2,6-Me2C6H3, 1) and polymeric catena-[Cu(µ-I)(CNC6H3-2-Cl-6-Me)2] (2) complexes with I2 at different molar ratios between the reactants resulted in a series of (RNC)2CuI-based crystal polyiodides formed along with gradual accumulation of iodine, namely the cocrystals [1·I2]·[Cu(µ1,1-I3)(CNXyl)2]2 followed by the generation of [Cu(µ1,3-I3)(CNXyl)2]2·2I2 (5·2I2) or [Cu(µ1,1-I3)(CNC6H3-2-Cl-6-Me)2]2 and then [Cu(µ1,3-I3)(CNC6H3-2-Cl-6-Me)2]n·n/2I2. The polyiodide 5·2I2 exhibits a novel supramolecular motif─a purely inorganic halogen-bonded Cu2(µ1,3-I3)2 core in the chair conformation. The X-ray structure of 5·2I2 featuring I···I contacts was analyzed by a set of theoretical methods and attributed to moderately strong halogen bonding (from -3.2 to -3.9 kcal/mol); these interactions determine the supramolecular architecture of 5·2I2.

12.
RSC Adv ; 13(48): 34064-34077, 2023 Nov 16.
Article in English | MEDLINE | ID: mdl-38019986

ABSTRACT

Two 1,3,4-oxadiazole-2-thione-N-Mannich derivatives, specifically 5-(4-chlorophenyl)-3-[(2-trifluoromethylphenylamino)methyl]-1,3,4-oxadiazole-2(3H)-thione (1) and 5-(4-chlorophenyl)-3-[(2,5-difluorophenylamino)methyl]-1,3,4-oxadiazole-2(3H)-thione (2), were synthesized and then characterized by elemental analysis and NMR (1H and 13C) spectroscopy and the single crystal X-ray diffraction method. The formed weak intermolecular interactions in the solid-state structures of these derivatives were thoroughly investigated utilizing a variety of theoretical tools such as Hirshfeld surface analysis and quantum theory of atoms in molecules (QTAIM). Furthermore, the CLP-PIXEL and density functional theory calculations were used to study the energetics of molecular dimers. Numerous weak intermolecular interactions such as C-H⋯S/Cl/F/π interactions, a directional C-Cl⋯Cl halogen bond, π-stacking, type C-F⋯F-C contact and a short F⋯O interaction, help to stabilize the crystal structure of 1. Crystal structure 2 also stabilizes with several weak intermolecular contacts, including N-H⋯S, C-H⋯N//Cl/F interactions, a highly directional C1-Cl1⋯C(π) halogen bond and C(π)⋯C(π) interaction. In vitro antimicrobial potency of compounds 1 and 2 was assessed against various Gram-positive and Gram-negative bacterial strains and the pathogenic yeast-like Candida albicans. Both compounds showed marked activity against all tested Gram-positive bacteria and weak activity against Escherichia coli and lacked inhibitory activity against Pseudomonas aeruginosa. In addition, compounds 1 and 2 displayed good in vitro anti-proliferative activity against hepatocellular carcinoma (HepG-2) and mammary gland breast cancer (MCF-7) cancer cell lines. Molecular docking studies revealed the binding modes of title compounds at the active sites of prospective therapeutic targets.

13.
RSC Adv ; 13(42): 29568-29583, 2023 Oct 04.
Article in English | MEDLINE | ID: mdl-37818264

ABSTRACT

Three cobalt complexes, namely [CoIII(HL1)2(N3)2]ClO4 (1), [CoIII(L2)(HL2)(N3)]ClO4·1.5H2O (2), and [CoIII(L3)(HL3)(NCS)]2 [CoIICl2(NCS)2] (3), where HL1 = 2-(3-(dimethylamino)propyliminomethyl)-6-methoxyphenol, HL2 = 2-(2-(dimethylamino)ethyliminomethyl)-4,6-dichlorophenol, and HL3 = 2-(2-(dimethylamino)ethyliminomethyl)-6-methoxyphenol, as potential tridentate N2O-donor Schiff base ligands, were synthesized and characterized using elemental analysis, IR and UV-vis spectroscopy, and single-crystal X-ray diffraction studies. All three were found to be monomeric ionic complexes. Complex 1 crystallizes in the orthorhombic space group Pbcn, whereas both complexes 2 and 3 crystallize in triclinic space groups, P1̄. Further, 1 and 2 are cationic complexes of octahedral cobalt(iii) with perchlorate anions, whereas complex 3 contains a cationic part of octahedral cobalt(iii) and an anionic part of tetrahedral cobalt(ii). Hydrogen-bonding interactions involving aromatic and aliphatic CH bonds as H-bond donors and the pseudo-halide co-ligands as H-bond acceptors were established, which are important aspects governing the X-ray packing. These interactions were analyzed theoretically using the quantum theory of atoms in molecules (QTAIM) and non-covalent interaction plot (NCI plot) analyses. Moreover, energy decomposition analysis (EDA) was performed to analyze the stabilization of the complexes in terms of the electrostatic, dispersion, and correlation forces.

14.
Dalton Trans ; 52(43): 15688-15696, 2023 Nov 07.
Article in English | MEDLINE | ID: mdl-37854010

ABSTRACT

In this manuscript we report the synthesis and X-ray characterization of two cyanidoaurate telluronium salts, namely (3-fluorophenyl)(methyl)(phenyl)telluronium dicyanidoaurate [(3-F-Ph)(Me)(Ph)Te][Au(CN)2] (1) and methyldiphenyltelluronium dicyanidoaurate [(Me)(Ph)2Te][Au(CN)2] (2). In the solid state, the tellurium atom establishes three concurrent and directional chalcogen bonds (ChBs) with the adjacent anions, in both compounds. These charge-assisted ChBs (CAChBs) have been analyzed using DFT calculations and several computational tools. The MEP surface analysis discloses the existence of three σ-holes at the Te-atoms capable of establishing strong CAChBs with the counter-ions. In addition, significant charge transfer from the lone pair orbital at the N-atom of the anion to the antibonding σ*(Te-C) orbital of the cation is observed in some cases.

15.
JACS Au ; 3(9): 2557-2565, 2023 Sep 25.
Article in English | MEDLINE | ID: mdl-37772186

ABSTRACT

Progress with fluorescent flippers, small-molecule probes to image membrane tension in living systems, has been limited by the effort needed to synthesize the twisted push-pull mechanophore. Here, we move to a higher oxidation level to introduce a new design paradigm that allows the screening of flipper probes rapidly, at best in situ. Late-stage clicking of thioacetals and acetals allows simultaneous attachment of targeting units and interfacers and exploration of the critical chalcogen-bonding donor at the same time. Initial studies focus on plasma membrane targeting and develop the chemical space of acetals and thioacetals, from acyclic amino acids to cyclic 1,3-heterocycles covering dioxanes as well as dithiolanes, dithianes, and dithiepanes, derived also from classics in biology like cysteine, lipoic acid, asparagusic acid, DTT, and epidithiodiketopiperazines. From the functional point of view, the sensitivity of membrane tension imaging in living cells could be doubled, with lifetime differences in FLIM images increasing from 0.55 to 1.11 ns. From a theoretical point of view, the complexity of mechanically coupled chalcogen bonding is explored, revealing, among others, intriguing bifurcated chalcogen bonds.

16.
Angew Chem Int Ed Engl ; 62(46): e202312223, 2023 Nov 13.
Article in English | MEDLINE | ID: mdl-37750233

ABSTRACT

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl3 or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.

17.
RSC Adv ; 13(31): 21313-21317, 2023 Jul 12.
Article in English | MEDLINE | ID: mdl-37456542

ABSTRACT

Despite debate on intramolecular N→P interactions in peri-substituted naphthalene derivatives their coordination chemistry has not yet been reported. Herein, we describe bonding in and reactivity of dichloro(8-dimethylamino-1-naphthyl)phosphane towards pentacarbonyltungsten(0) reagents. A 1-aza-2-phospha-acenaphthene complex was obtained via the unexpected elimination of chloromethane enabled through P-coordination. Theoretical DFT calculations provide insights into P⋯N pnictogen bonding interaction as well as the reaction pathway of the elimination reaction.

18.
RSC Adv ; 13(31): 21211-21224, 2023 Jul 12.
Article in English | MEDLINE | ID: mdl-37456548

ABSTRACT

Four manganese(iii) complexes, [MnL1(H2O)2]ClO4·H2O (1), [MnL2(H2O)2]ClO4 (2), [MnL3(DMSO)(H2O)]ClO4 (3) and [MnL4(DMSO)(H2O)]ClO4 (4), where H2L1 = N,N'-bis(5-bromosalicylidene)-1,3-diaminopropane, H2L2 = 2,2-dimethyl-N,N-bis(3-methyloxysalicylidene)-1,3-diaminopropane, H2L3 = N,N'-bis(5-chlorosalicylidene)-2,2-dimethyl-1,3-diaminopropane and H2L4 = 2-hydroxy-N,N'-bis(3-ethyloxysalicylidene)-1,3-diaminopropane are tetradentate N2O2-donor ligands and DMSO = dimethyl sulfoxide, have been synthesized and characterised by elemental analysis, IR and UV-vis spectroscopy and single-crystal X-ray diffraction studies. All are monomeric complexes. Complex 1 crystallises in orthorhombic space group P212121, complex 3 crystallises in triclinic space group P-1, whereas complexes 2 and 4 crystallize in monoclinic space groups, C2/c and C2/m respectively. In all the complexes, manganese(iii) has a six-coordinated pseudo-octahedral geometry in which imine nitrogen atoms and phenolate oxygen atoms of the deprotonated di-Schiff base constitute the equatorial plane. In complexes 1 and 2, water molecules are present in the fifth and sixth coordination sites in the axial positions while in complexes 3 and 4 they are occupied by one water and one DMSO. The coordinated water molecules initiate hydrogen-bonded networks in all complexes. DFT calculations have been carried out to analyze two aspects of these complexes viz. the formation of halogen (HaB) and chalcogen bonding (ChB) interactions in complexes 1 and 3 where the electron donor is the perchlorate anion and the acceptor either bromine or chlorine atoms for the HaBs and the sulfur atom of the coordinated DMSO for the ChB. In addition, other intermolecular effects are discussed in the solid state for complexes 1, 2 and 4, where the hydrogen atoms of the coordinated water molecules interact with the electron rich cavities formed by the phenolate and alkyloxy oxygen atoms of the Schiff-base ligand.

19.
Chemistry ; 29(60): e202302176, 2023 Oct 26.
Article in English | MEDLINE | ID: mdl-37518768

ABSTRACT

Analyses of the Cambridge Structural Database and theoretical calculations (PBE0-D3/def2-TZVP level, atoms-in-molecules, natural bond orbital studies) prove the formation of net attractive noncovalent interactions between group 5 elements and electron-rich atoms (neutral or anionic). These kinds of bonding are markedly different from coordination bonds formed by the same elements and possess the distinctive features of σ-hole interactions. The term erythronium bond is proposed to denote these bonds. X-ray structures of vanadate-dependent bromoperoxidases show that these interactions are present also in biological systems.

20.
Inorg Chem ; 62(19): 7131-7140, 2023 May 15.
Article in English | MEDLINE | ID: mdl-37139684

ABSTRACT

The synthesis of fluorescein propargyl diether (L) and two different dinuclear gold(I) derivatives containing a water-soluble phosphane [1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane (PTA) for complex 1 and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) for complex 2] has been successfully performed. All compounds display intrinsic emission from fluorescein, being less intense for gold(I) complexes due to the heavy-atom effect. All compounds aggregate in acetonitrile/water mixtures with the formation of larger aggregates for those samples containing more water content, as evidenced by dynamic light scattering and small-angle X-ray scattering experiments, in agreement with the absorption and emission data. The emission of the samples increases when they are used to obtain luminescent materials with four different organic matrices [poly(methyl methacrylate, polystyrene (PS), cellulose, and Zeonex]. The compounds display very high values of singlet oxygen (1O2) production in dichloromethane. Singlet oxygen production was also evaluated in the doped matrices, being the highest in PS and with an exciting increase on PS microspheres. Density functional theory (BP86-D3) and GFN2-xTB calculations were used to model the assembly of L and complexes 1 and 2 with the different organic matrices and rationalize the experimental findings based on the geometries, molecular electrostatic potential surfaces, and complementarity and HOMO-LUMO gaps.

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