A general strategy to study the thermodynamics of ligand adsorption to colloidal surfaces was established. The versatility of our approach is demonstrated by means of catechols binding to ZnO quantum dots (QDs). First, isothermal titration calorimetry (ITC) was used to extract all relevant thermodynamic parameters, namely association constant, enthalpy, entropy, and free energy of ligand binding. Noteworthy, the determined ΔG of −20.3 ± 0.4 kJ mol −1 indicates a strong, reproducible, and exothermic interaction between the catechol anchor group and the oxide particle surface. To confirm the characterization of ligand binding by measuring the heat of adsorption, the free energy was crossvalidated by mass-based adsorption isotherms. A combination of inductively coupled plasma optical emission spectroscopy (ICP-OES) and UV/vis spectroscopy was developed to quantitatively determine the mass of bound catechols with respect to the available particle surface. The association constant K was determined by a Langmuir fit to be 2618 M −1 which leads to ΔG = −19.50 kJ mol −1 according to ΔG = −RTln K. To close the mass balance, analytical ultracentrifugation (AUC) was applied to detect the amount of the free, unbound catechol in solution. Finally, Raman spectroscopy and nuclear magnetic resonance spectroscopy (NMR) were performed to quantify the amount of remaining acetate from particle synthesis and to distinguish bound (chemisorbed) and unbound (physisorbed) catechol. Our results reveal that approximately 65 wt % of acetate is replaced, and physisorbed catechol will not affect the amount of remaining acetate on the ZnO surface. Moreover, no pronounced chemical shift peak as it would be expected for free catechol is observed by NMR at all. This indicates a highly dynamic adsorption−desorption equilibrium between the free and the physisorbed state of catechol on the particle surface. Our concept of combined analytics is seen to be a generally applicable strategy for particle-ligand interfacial studies. It gives detailed insight into thermodynamics, binding states, and ligand composition and is thus considered as an important step toward tailored colloidal surface properties.

The differences in the electroluminescence (EL) of red‐emitting free‐base (H2TPP) and Zn‐metalated (ZnTPP) archetypal porphyrins are rationalized in light‐emitting electrochemical cells by means of an electric‐field dependent effect, leading to whitish and reddish devices, respectively. Although H2TPP shows superior electrochemical and photophysical features compared to ZnTPP, devices prepared with ZnTPP surprisingly stand out with a deep‐red EL similar to its photoluminescence (PL), while H2TPP devices feature unexpected whitish EL. Standard arguments such as degradation, device architecture, device mechanism, and changes in the nature of the emitting excited states are discarded. Based on electrochemical impedance spectroscopy and first‐principles electronic structure methods, we provide evidence that the EL originates from two H2TPP regioisomers, in which the inner ring H atoms are placed in collinear and vicinal configurations. The combination of their optical features provides an explanation for both the high‐ and low‐energy EL features. Here, the emitting excited state nature is ascribed to the Q bands, since the Soret excited states remain high in energy. This contrasts to what is traditionally postulated in reports focused on H2TPP lighting devices. Hence, this work provides a new explanation for the nature of the high‐energy EL band of H2TPP that might inspire future works focused on white‐emitting molecular‐based devices.

In the current work, we present the successful functionalization and stabilization of P-25 TiO2 nanoparticles by means of N1,N7-bis(3-(4-tert-butyl-pyridium-methyl)phenyl)-4-(3-(3-(4-tert-butyl-pyridinium-methyl)phenylamino)-3-oxopropyl)-4-(3,4-dihydroxybenzamido)heptanediamide tribromide (1). The design of the latter is aimed at nanoparticle functionalization and stabilization with organic building blocks. On one hand, 1 features a catechol anchor to enable its covalent grafting onto the TiO2 surface, and on the other hand, positively charged pyridine groups at its periphery to prevent TiO2 agglomeration through electrostatic repulsion. The success of functionalization and stabilization was corroborated by thermogravimetric analysis, dynamic light-scattering, and zeta potential measurements. As a complement to this, the formation of layer-by-layer assemblies, which are governed by electrostatic interactions, by alternate deposition of functionalized TiO2 nanoparticles and two negatively charged porphyrin derivatives, that is, 5,10,15,20-(phenoxyacetic acid)-porphyrin (2) and 5,10,15,20-(4-(2-ethoxycarbonyl)-4-(2-phenoxyacetamido)heptanedioic acid)-porphyrin (3), is documented. To this end, the layer-by-layer deposition is monitored by UV/Vis spectroscopy, scanning electron microscopy, ellipsometry, and profilometry techniques. The resulting assemblies are utilized for the construction and testing of novel solar cells. From stable and repeatable photocurrents generated during several "on-off" cycles of illumination, we derive monochromatic incident photo-to-current conversion efficiencies of around 3 %.

We present the formation of individualized and stabilized zinc oxide (ZnO) nanorods by functionalization with positively charged catechol derivatives by means of ligand exchange reactions. The electrosteric stabilization of ZnO nanorods was studied using two catechol derivatives, introducing either three (1) or six (2) pH independent positive charges per molecule and sterically demanding groups onto the surface. ZnO nanorods providing initially acetate (Ac) or 2-[2-(2-methoxyethoxy)-ethoxy]acetic acid (TODA) ligands on their surface were used. The ligand exchange was performed by using mono and mixed functionalization approaches, utilizing either exclusively the positively charged catechols or mixtures of the latter with small commercially available catechol derivatives, namely 4-methylcatechol (Me-cat), 4-tert-butylcatechol (tBu-cat), and dopamine hydrochloride (Dop). Using a combination of various analytical methods such as zeta potential, dynamic light scattering (DLS), UV/Vis, and scanning electron microscopy (SEM) measurements we found that the initial surfactants on the nanorods surface, the number of positive charges per molecule, the steric demand, and the added amount of the catechol derivative strongly influence the colloidal behavior of the nanorods. Stable suspensions containing individualized ZnO nanorods were successfully formed upon functionalization of ZnO-TODA nanorods with 30 monolayers (MLs) of the higher charged catechol (2), as well as using mixtures of 20/10 and 18/10 MLs of 2/Dop.

To optimize electron transfer and optoelectronic properties in nanoparticulate thin films for electronics we show the surface functionalization of ZnO nanorods by means of replacing surface active 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (TODA) by a redoxactive organic component, that is, 5,10,15,20-(phenoxyacetat)-porphyrin bearing four carboxylic acids as possible ZnO anchors. Microscopy-transmission electron microscopy-and spectroscopy-optical spectroscopy-verifies the successful and homogenous integration of the porphyrin onto the surface of ZnO nanorods, a process that is facilitated by the four anchoring groups. Photophysical investigations based on emission and absorption spectroscopy prompt to distinct electronic interactions between ZnO nanorods and the porphyrins. Consequently, we performed further photophysical studies flanked by pulse radiolysis assays to corroborate the nature of the electronic interactions.