Two‐Photon‐Induced CO‐Releasing Molecules as Molecular Logic Systems in Solution, Polymers, and Cells

Abstract

Phototherapeutic applications of carbon monoxide (CO)‐releasing molecules are limited because they require harmful UV and blue light for activation. We describe two‐photon excitation with NIR light (800 nm)‐induced CO‐release from two MnI tricarbonyl complexes bearing 1,8‐naphthalimide units (1, 2). Complex 2 behaves as a logic OR gate in solution, nonwovens, and in HeLa cells. CO release, indicated by fluorescence enhancement, was detected in solution, nonwoven, and HeLa cells by single‐ (405 nm) and two‐photon (800 nm) excitation. The photophysical properties of 1 and 2 have been measured and supported by DFT and TDDFT quantum chemical calculations. Both photoCORMs are stable in the dark in solution and noncytotoxic, leading to promising applications as phototherapeutics with NIR light.

Release of CO and Production of 1O2 from a Mn-BODIPY Photoactivated CO Releasing Molecule with Visible Light

“…One of the main challenges in designing an efficient photoCORM is activation by light in the phototherapeutic window (600–950 nm). To date, various strategies, including ancillary ligand modifications, , multiphoton excitation, , mixing with a triplet-state photosensitizer, quantum dots, upconverting nanoparticles, or as previously reported by our group, coupling with a visible light absorbing metal complex, and so forth, have been employed to activate the photo-CO dissociation under visible and NIR irradiation. Alternatively, the use of dye photosensitizers as light-harvesting components of the design allows for visible light-activated photoCORMs …”

Metal-free carbon monoxide-releasing micelles undergo tandem photochemical reactions for cutaneous wound healing

“…[7][8][9][10] These CORMs can be roughly categorized into two sorts, namely metal carbonyls and metal-free CORMs. Although metal carbonyls hold great promise in both laboratory and clinical investigations, 9,[11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] the development of metal-free CORMs has recently been receiveing increasing attention. 27 In this context, boranocarbonates, 28 CO-releasing prodrugs operated in a "click and release" manner, [29][30][31] and photoresponsive organic CORMs such as 3-hydroxyavone (3-HF) derivatives, [32][33][34][35][36][37] xanthene-9-carboxylic acid, 38 BODIPY derivatives, 39 and aromatic a-diketone derivatives 40 have been developed.…”

Near-Infrared and Visible Photoactivation to Uncage Carbon Monoxide from an Aqueous-Soluble PhotoCORM

“…The tpy functionality serves as the attachment site to a manganese­(I) carbonyl fragment, and this combination elicits two-photon activated CO release with NIR. Notably, during the preparation of these results for publication, another laboratory independently reported the generation of CO via the TPE of a manganese carbonyl complex …”

“…Notably, during the preparation of these results for publication, another laboratory independently reported the generation of CO via the TPE of a manganese carbonyl complex. 35 ■ RESULTS AND DISCUSSION Synthesis and Characterization. The general synthesis of the complexes Mn(CO) 3 (η 2 -TPYOH)X, X = Br − (1) or CF 3 SO 3 − (2), is presented in Scheme 1.…”