Insights into NdIII to YbIII Energy Transfer and Its Implications in Luminescence Thermometry.

This work challenges the conventional approach of using NdIII 4F3/2 lifetime changes for evaluating the experimental NdIII → YbIII energy transfer rate and efficiency. Using near-infrared (NIR) emitting Nd:Yb mixed-metal coordination polymers (CPs), synthesized via solvent-free thermal grinding, we demonstrate that the NdIII [2H11/2 → 4I15/2] → YbIII [2F7/2 → 2F5/2] pathway, previously overlooked, dominates energy transfer due to superior energy resonance and J-level selection rule compatibility. This finding upends the conventional focus on the NdIII [4F3/2 → 4I11/2] → YbIII [2F7/2 → 2F5/2] transition pathway. We characterized Nd0.890Yb0.110(BTC)(H2O)6 as a promising cryogenic NIR thermometry system and employed our novel energy transfer understanding to perform simulations, yielding theoretical thermometric parameters and sensitivities for diverse Nd:Yb ratios. Strikingly, experimental thermometric data closely matched the theoretical predictions, validating our revised model. This novel perspective on NdIII → YbIII energy transfer holds general applicability for the NdIII/YbIII pair, unveiling an important spectroscopic feature with broad implications for energy transfer-driven materials design.

Luminescent Ln3+-based silsesquioxanes with a ß-diketonate antenna ligand: toward the design of efficient temperature sensors.

We report the synthesis and single-crystal X-ray diffraction, magnetic, and luminescence measurements of a novel family of luminescent cage-like tetranuclear silsesquioxanes (PhSiO1.5)8(LnO1.5)4(O)(C5H8O2)6(EtOH)2(CH3CN)2⋅2CH3CN (where Ln = Tb, 1; Tb/Eu, 2; and Gd, 3), featuring seven-coordinated lanthanide ions arranged in a one-capped trigonal prism geometry. Compounds 1 and 2 exhibit characteristic Tb3+ and Tb3+/Eu3+-related emissions, respectively, sensitized by the chelating antenna acetylacetonate (acac) ligands upon excitation in the UV and visible spectral regions. Compound 3 is used to assess the energies of the triplet states of the acac ligand. For compound 1, theoretical calculations on the intramolecular energy transfer and multiphonon rates indicate a thermal balance between the 5D4 Stark components, while the mixed Tb3+/Eu3+ analog 2, with a Tb:Eu ratio of 3:1, showcases intra-cluster Tb3+-to-Eu3+ energy transfer, calculated theoretically as a function of temperature. By utilizing the intensity ratio between the 5D4→7F5 (Tb3+) and 5D0→7F2 (Eu3+) transitions in the range 11-373 K, we demonstrate the realization of a ratiometric luminescent thermometer with compound 2, operating in the range 11-373 K with a maximum relative sensitivity of 2.0% K-1 at 373 K. These findings highlight the potential of cage-like silsesquioxanes as versatile materials for optical sensing-enabled applications.

Correction: Carbon dots on LAPONITE® hybrid nanocomposites: solid-state emission and inter-aggregate energy transfer.

Correction for 'Carbon dots on LAPONITE® hybrid nanocomposites: solid-state emission and inter-aggregate energy transfer' by Bruno S. D. Onishi et al., Nanoscale, 2024, https://doi.org/10.1039/d3nr06336d.

Carbon dots on LAPONITE® hybrid nanocomposites: solid-state emission and inter-aggregate energy transfer.

This study delves into the photoluminescent characteristics of solid-state hybrid carbon dots/LAPONITE® (CDLP). These hybrid materials were synthesized using the hydrothermal method with a precise pH control set at 8.5. The LAPONITE® structure remains intact without structural collapse, and we detected the possible deposition of carbon dots (CDs) aggregates on the clay mineral's edges. The use of different concentrations of citric acid (10-, 6-, 2- and 1-times weight/weight of LAPONITE® mass, maintaining the 1 : 1 molar ratio with ethylenediamine) during synthesis results in different CDs concentrations in CDLP-A (low precursors concentration) and CDLP-D (high concentration) with an amorphous structure and average size around 2.8-3.0 nm. The CDLP displayed visible photoluminescence emission in aqueous and powder, which the last underwent quenching according to lifetimes and quantum yield measurements. Low-temperature measurements revealed an enhancement of the non-radiative pathways induced by aggregation. Energy transfer modelling based on Förster-Dexter suggests an approximate mean distance of 9.5 nm between clusters of CDs.

Tuning the Emission of Homometallic DyIII, TbIII, and EuIII 1-D Coordination Polymers with 2,6-Di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo Ligands: Sensitization through the Singlet State.

This work reports the structural characterization and photophysical properties of DyIII, TbIII, and EuIII coordination polymers with two phenoxo-triazole-based ligands [2,6-di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo, LRTr (R = CH3; Cl)]. These ligands permitted us to obtain isostructural polymers, described as a 1D double chain, with LnIII being nona-coordinated. The energies of the ligand triplet (T1) states were estimated using low-temperature time-resolved emission spectra of YIII analogues. Compounds with LClTr present higher emission intensity than those with LMeTr. The emission of TbIII compounds was not affected by the different excitation wavelengths used and was emitted in the pure green region. In contrast, DyLMeTr emits in the blue-to-white region, while the luminescence of DyLClTr remains in the white region for all excitation wavelengths. On the other hand, EuIII compounds emit in the blue (ligand) or red region (EuIII) depending on the substituent of the phenoxo moiety and excitation wavelength. Theoretical calculations were employed to determine the excited states of the ligands by using time-dependent density functional theory. These calculations aided in modeling the intramolecular energy transfer and rationalizing the optical properties and demonstrated that the sensitization of the LnIII ions is driven via S1 → LnIII, a process that is less common as compared to T1 → LnIII.

Hybrid multifunctionalized mesostructured stellate silica nanoparticles loaded with ß-diketonate Tb3+/Eu3+ complexes as efficient ratiometric emissive thermometers working in water.

Despite the great effort made in recent years on lanthanide-based ratiometric luminescent nanothermometers able to provide temperature measurements in water, their design remains challenging. We report on the synthesis and properties of efficient ratiometric nanothermometers that are based on mesoporous stellate nanoparticles (MSN) of ca. 90 nm functionalized with an acetylacetonate (acac) derivative inside the pores and loaded with ß-diketonate-Tb3+/Eu3+ complexes able to work in water, in PBS or in cells. Encapsulating a [(Tb/Eu)9(acac)16(µ3-OH)8(µ4-O)(µ4-OH)] complex (Tb/Eu ratio = 19/1 and 9/1) led to hybrid multifunctionalized nanoparticles exhibiting a Tb3+ and Eu3+ characteristic temperature-dependent luminescence with a high rate Tb3+-to-Eu3+ energy transfer. According to theoretical calculations, the modifications of photoluminescence properties and the increase in the pairwise Tb3+-to-Eu3+ energy transfer rate by about 10 times can be rationalized as a change of the coordination number of the Ln3+ sites of the complex from 7 to 8 accompanied by a symmetry evolution from Cs to C4v and a slight shortening of intramolecular Ln3+-Ln3+ distances upon the effect of encapsulation. These nanothermometers operate in the 20-70 °C range with excellent photothermal stability, cyclability and repeatability (>95%), displaying a maximum relative thermal sensitivity of 1.4% °C-1 (at 42.7 °C) in water. Furthermore, they can operate in cells with a thermal sensitivity of 8.6% °C-1 (at 40 °C), keeping in mind that adjusting the calibration for each system is necessary to ensure accurate measurements.

Spotlight on Luminescence Thermometry: Basics, Challenges, and Cutting-Edge Applications.

Luminescence (nano)thermometry is a remote sensing technique that relies on the temperature dependency of the luminescence features (e.g., bandshape, peak energy or intensity, and excited state lifetimes and risetimes) of a phosphor to measure temperature. This technique provides precise thermal readouts with superior spatial resolution in short acquisition times. Although luminescence thermometry is just starting to become a more mature subject, it exhibits enormous potential in several areas, e.g., optoelectronics, photonics, micro- and nanofluidics, and nanomedicine. This work reviews the latest trends in the field, including the establishment of a comprehensive theoretical background and standardized practices. The reliability, repeatability, and reproducibility of the technique are also discussed, along with the use of multiparametric analysis and artificial-intelligence algorithms to enhance thermal readouts. In addition, examples are provided to underscore the challenges that luminescence thermometry faces, alongside the need for a continuous search and design of new materials, experimental techniques, and analysis procedures to improve the competitiveness, accessibility, and popularity of the technology.

Eu3+ and Tb3+ coordination compounds with phenyl-containing carbacylamidophosphates: comparison with selected Ln3+ ß-diketonates.

Materials based on Eu3+ and Tb3+ coordination compounds are of great interest due to their strong red and green luminescence. Appropriate selection of ligands plays a huge role in optimizing their photophysical properties. Another very helpful instrument for such optimization is theoretical modelling, which permits the prediction of the emissive properties of materials through intramolecular energy transfer analysis. The ligands that allow for achieving high efficiency of Eu3+ and Tb3+ emissions include carbacylamidophosphates (CAPh, HL). In this brief review, we summarize recent research for lanthanides CAPh-based coordination compounds of general formulas Cat[LnL]4, [LnL3Q] and [Ln(HL)3(NO3)3], where Cat+ = Cs+, NEt4+, PPh4 + and Q = 1,10-phenanthroline, 2,2-bipyridine or triphenylphosphine oxide, involving the use of thermal gravimetric analysis, X-ray analysis, and absorption and luminescence spectroscopy. We carried out a comparison with selected Ln3+ ß-diketonates. Possibilities and developments of theoretical calculations on energy transfer rates are also presented.

Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae.

In this work, we investigated from a theoretical point of view the dynamics of the energy transfer process from the ligand to Eu(III) ion for 12 isomeric species originating from six different complexes differing by nature of the ligand and the total charge. The cationic complexes present the general formula [Eu(L)(H2O)2]+ (where L = bpcd2- = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate; bQcd2- = N,N'-bis(2-quinolinmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate; and bisoQcd2- = N,N'-bis(2-isoquinolinmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate), while the neutral complexes present the Eu(L)(H2O)2 formula (where L = PyC3A3- = N-picolyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetate; QC3A3- = N-quinolyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetate; and isoQC3A3- = N-isoquinolyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetate). Time-dependent density functional theory (TD-DFT) calculations provided the energy of the ligand excited donor states, distances between donor and acceptor orbitals involved in the energy transfer mechanism (RL), spin-orbit coupling matrix elements, and excited-state reorganization energies. The intramolecular energy transfer (IET) rates for both singlet-triplet intersystem crossing and ligand-to-metal (and vice versa) involving a multitude of ligand and Eu(III) levels and the theoretical overall quantum yields (ϕovl) were calculated (the latter for the first time without the introduction of experimental parameters). This was achieved using a blend of DFT, Judd-Ofelt theory, IET theory, and rate equation modeling. Thanks to this study, for each isomeric species, the most efficient IET process feeding the Eu(III) excited state, its related physical mechanism (exchange interaction), and the reasons for a better or worse overall energy transfer efficiency (ηsens) in the different complexes were determined. The spectroscopically measured ϕovl values are in good agreement with the ones obtained theoretically in this work.

Magneto-Induced Hyperthermia and Temperature Detection in Single Iron Oxide Core-Silica/Tb3+/Eu3+(Acac) Shell Nano-Objects.

Multifunctional nano-objects containing a magnetic heater and a temperature emissive sensor in the same nanoparticle have recently emerged as promising tools towards personalized nanomedicine permitting hyperthermia-assisted treatment under local temperature control. However, a fine control of nano-systems' morphology permitting the synthesis of a single magnetic core with controlled position of the sensor presents a main challenge. We report here the design of new iron oxide core-silica shell nano-objects containing luminescent Tb3+/Eu3+-(acetylacetonate) moieties covalently anchored to the silica surface, which act as a promising heater/thermometer system. They present a single magnetic core and a controlled thickness of the silica shell, permitting a uniform spatial distribution of the emissive nanothermometer relative to the heat source. These nanoparticles exhibit the Tb3+ and Eu3+ characteristic emissions and suitable magnetic properties that make them efficient as a nanoheater with a Ln3+-based emissive self-referencing temperature sensor covalently coupled to it. Heating capacity under an alternating current magnetic field was demonstrated by thermal imaging. This system offers a new strategy permitting a rapid heating of a solution under an applied magnetic field and a local self-referencing temperature sensing with excellent thermal sensitivity (1.64%·K-1 (at 40 °C)) in the range 25-70 °C, good photostability, and reproducibility after several heating cycles.

Tunable Optical Molecular Thermometers Based on Metallacrowns.

The effect of ligands' energy levels on thermal dependence of lanthanide emission was examined to create new molecular nanothermometers. A series of Ln2Ga8L8'L8″ metallacrowns (shorthand Ln2L8'), where Ln = Gd3+, Tb3+, or Sm3+ (H3L' = salicylhydroxamic acid (H3shi), 5-methylsalicylhydroxamic acid (H3mshi), 5-methoxysalicylhydroxamic acid (H3moshi), and 3-hydroxy-2-naphthohydroxamic acid (H3nha)) and H2L″ = isophthalic acid (H2iph), was synthesized and characterized. Within the series, ligand-centered singlet state (S1) energy levels ranged from 23,300 to 27,800 cm-1, while triplet (T1) energy levels ranged from 18,150 to 21,980 cm-1. We demonstrated that the difference between T1 levels and relevant energies of the excited 4G5/2 level of Sm3+ (17,800 cm-1) and 5D4 level of Tb3+ (20,400 cm-1) is the major parameter controlling thermal dependence of the emission intensity via the back energy transfer mechanism. However, when the energy difference between S1 and T1 levels is small (below 3760 cm-1), the S1 → T1 intersystem crossing (and its reverse, S1 ← T1) mechanism contributes to the thermal behavior of metallacrowns. Both mechanisms affect Ln3+-centered room-temperature quantum yields with values ranging from 2.07(6)% to 31.2(2)% for Tb2L8' and from 0.0267(7)% to 2.27(5)% for Sm2L8'. The maximal thermal dependence varies over a wide thermal range (ca. 150-350 K) based on energy gaps between relevant ligand-based and lanthanide-based electronic states. By mixing Tb2moshi8' with Sm2moshi8' in a 1:1 ratio, an optical thermometer with a relative thermal sensitivity larger than 3%/K at 225 K was created. Other temperature ranges are also accessible with this approach.

Enhancing the Luminescence of Eu(III) Complexes with the Ruthenocene Organometallic Unit as Ancillary Ligand.

Five novel Eu(III)-ß-diketonate complexes containing ruthenocene ancillary ligands (1,1'-bis(diphenylphosphoryl)ruthenocene─RcBPO) were synthesized and characterized. The coordination compounds presented the general formula [Eu(ß-dik)3(RcBPO)], where ß-dik stands for 2-thenoyltrifluoroacetonate (tta), 3-benzoyl-1,1,1-trifluoroacetone (btf), 2-dibenzoylmethanate (dbm), 2-acetyl-1,3-indandionate (aind), and 2-benzoyl-1,3-indandionate (bind), and RcBPO stands for 1,1'-bis(diphenylphosphoryl)ruthenocene. The [Eu(aind)3(RcBPO)] complex crystallizes in a monoclinic Cc non-centrosymmetric space group with the europium site environment, assuming a bicapped trigonal prism coordination polyhedron with the symmetry point group close to C2v. Photoluminescent properties for the solid-state samples were described in terms of excitation, emission, lifetime decay curves, and intrinsic and overall quantum yields. The replacement of the two coordinated H2O molecules by the RcBPO ancillary ligand leads to great enhancements of the overall quantum yields (QEuL), with the minimum increment by a factor of 5 for the case of [Eu(btf)3(RcBPO)] and the maximum enhancement of 270 times for the case of the [Eu(dbm)3(RcBPO)] complex. In addition, theoretical calculations were carried out to model the spectroscopic properties of the investigated compounds. To obtain theoretical Judd-Ofelt parameters (Ωλ, λ = 2, 4, and 6) and intramolecular energy transfer rates, the JOYSpectra web platform was employed using the structure obtained from density functional theory calculations. Hence, a rate equation model provided theoretical overall quantum yields, which are in great agreement with measured data.

New Luminescent Lanthanide Tetrakis-Complexes NEt4 [LnL4 ] Based on Dimethyl-N-Benzoylamidophosphate.

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt4 [LnL4 ] (Ln3+ =La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt4+ on the structure and properties of the tetrakis-complex [LnL4]- is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of 5 D0 →7 F4 transition, observed in the luminescence spectrum of NEt4 [EuL4 ], is discussed based on theoretical calculations.

Spectroscopic aspects for the Yb3+ coordination compound with a large energy gap between the ligand and Yb3+ excited states.

We present the experimental and theoretical results that made it possible to propose the energy transfer mechanism for a Yb complex with a large energy gap between the ligand and Yb excited states using a theoretical model and experimental data. Absorption and emission spectroscopy in the 300-4 K range is used for the study of the Yb3+ compound with N-phosphorylated sulfonamide (Na[YbL4]), which, despite the large energy gap, is characterized by high emission sensitization efficiency (ηsens = 40%) and relatively long Yb3+ emission lifetime (27 µs). The crystal structure of Na[YbL4], radiative lifetime (930 µs), refractive index (1.46), intrinsic (3.0%), and overall (1.3%) emission quantum yield were determined. To obtain the electronic properties of the Na[YbL4], a time-dependent density functional theory (TD-DFT) was performed. The intramolecular energy transfer (IET) rates from the excited states S1 and T1 to the Yb3+ ion as well as between the ligand and the ligand-to-metal charge transfer (LMCT) states were calculated. Once the intersystem crossing S1 â†’ T1 is not so effective due to a large energy gap between S1 and T1 (≈10000 cm-1), it has been shown that the LMCT state acts as an additional channel to feed the T1 state. Then, the T1 can transfer energy to the Yb3+ 2F5/2 energy level (WT), where WT is dominated by the exchange mechanism. Based on IET and a rate equation model, the overall emission quantum yield QLLn was simulated with and without the LMCT, this also confirmed that the pathway S1 â†’ LMCT â†’ T1 â†’ Yb3+ is more likely than the S1 â†’ T1 â†’ Yb3+ one.

First complete NMR data and theoretical study of an antimicrobial formylated dihydrochalcone from Psidium guineense Sw.

Chalcones are a widespread group of natural compounds characterized by the basic structure 1,3-diaryl-2-propen-1-one. In this study, we focused on the uncommon formylated chalcone 3'-formyl-2',4',6'-trihydroxy-5'-methyldihydrochalcone that possess interesting antimicrobial and anticancer potential. Considering the pharmacological relevance of this compound, we report its isolation and the first complete and unequivocal NMR data for this substance, corroborated by in silico theoretical study. In addition to that, its antibacterial potential was evaluated and the compound presented strong activity against Pseudomonas aeruginosa.[Formula: see text].

Controlling the thermal switching in upconverting nanoparticles through surface chemistry.

Photon upconversion taking place in small rare-earth-doped nanoparticles has been recently observed to be thermally modulated in an anomalous manner, showing thermal enhancement of the emission intensity. This effect was proved to be linked to the role of adsorbed water molecules as surface quenchers. The surface capping of the particles has a direct influence on the thermal dynamics of water adsorption and desorption, and therefore on the optical properties. Here, we show that the upconversion intensity of small-size (<25 nm) nanoparticles co-doped with Yb3+ and Er3+ ions, and functionalized with different capping molecules, presents clear irreversibility patterns upon thermal cycling that strongly depend on the chemical nature of the nanoparticle surface. By performing temperature-controlled luminescence measurements we observed the formation of a thermal hysteresis loop, resembling an optical switching phenomenon, whose shape and trajectory depend on the hydrophilicity of the surface. Additionally, an intensity overshoot takes place immediately after turning off the heating source, affecting each radiative transition differently. We performed numerical modelling to understand this effect considering non-radiative energy transfer from the surface defect states to the Er3+ ions. These findings are relevant for the comprehension of nanoparticle-based luminescence and the interplay between the surface and volume effects, and more generally, for applications involving UCNPs such as nanothermometry and bioimaging, and the development of optical encoding systems.

Surface Plasmon-Photon Coupling in Lanthanide-Doped Nanoparticles.

Lanthanide-doped nanoparticles have great potential for energy conversion applications, as their optical properties can be precisely controlled by varying the doping composition, concentration, and surface structures, as well as through plasmonic coupling. In this Perspective we highlight recent advances in upconversion emission modulation enabled by coupling upconversion nanoparticles with well-defined plasmonic nanostructures. We emphasize fundamental understanding of luminescence enhancement, monochromatic emission amplification, lifetime tuning, and polarization control at nanoscale. The interplay between localized surface plasmons and absorbed photons at the plasmonic metal-lanthanide interface substantially enriches the interpretation of plasmon-coupled nonlinear photophysical processes. These studies will enable novel functional nanomaterials or nanostructures to be designed for a multitude of technological applications, including biomedicine, lasing, optogenetics, super-resolution imaging, photovoltaics, and photocatalysis.

Seven-Coordinate Tb3+ Complexes with 90% Quantum Yields: High-Performance Examples of Combined Singlet- and Triplet-to-Tb3+ Energy-Transfer Pathways.

Seven-coordinate, pentagonal-bipyramidal (PBP) complexes [Ln(bbpen)Cl] and [Ln(bbppn)Cl], in which Ln = Tb3+ (products I and II), Eu3+ (III and IV), and Gd3+ (V and VI), with bbpen2- = N,N'-bis(2-oxidobenzyl)-N,N'-bis(pyridin-2-ylmethyl)ethylenediamine and bbppn2- = N,N'-bis(2-oxidobenzyl)-N,N'-bis(pyridin-2-ylmethyl)-1,2-propanediamine, were synthesized and characterized by single-crystal X-ray diffraction analysis, alternating-current magnetic susceptibility measurements, and photoluminescence (steady-state and time-resolved) spectroscopy. Under a static magnetic field of 0.1 T, the Tb3+ complexes I and II revealed single-ion-magnet behavior. Also, upon excitation at 320 nm at 300 K, I and II presented very high absolute emission quantum yields (0.90 ± 0.09 and 0.92 ± 0.09, respectively), while the corresponding Eu3+ complexes III and IV showed no photoluminescence. Detailed theoretical calculations on the intramolecular energy-transfer rates for the Tb3+ products indicated that both singlet and triplet ligand excited states contribute efficiently to the overall emission performance. The expressive quantum yields, QLnL, measured for I and II in the solid state and a dichloromethane solution depend on the excitation wavelength, being higher at 320 nm. Such a dependence was rationalized by computing the intersystem crossing rates (WISC) and singlet fluorescence lifetimes (τS) related to the population dynamics of the S1 and T1 levels. Thin films of product II showed high air stability and photostability upon continuous UV illumination, which allowed their use as downshifting layers in a green light-emitting device (LED). The prototypes presented a luminous efficacy comparable with those found in commercial LED coatings, without requiring encapsulation or dispersion of II in host matrixes. The results indicate that the PBP environment determined by the ethylenediamine (en)-based ligands investigated in this work favors the outstanding optical properties in Tb3+ complexes. This work presents a comprehensive structural, chemical, and spectroscopic characterization of two Tb3+ complexes of mixed-donor, en-based ligands, focusing on their outstanding optical properties. They constitute good molecular examples in which both triplet and singlet excited states provide energy to the Tb3+ ion and lead to high values of QLnL.

Overlap properties of chemical bonds in generic systems including unusual bonding situations.

Chemical bond is a ubiquitous and fundamental concept in chemistry, in which the overlap plays a defining role. By using a new approach based on localized molecular orbitals, the overlap properties, e.g., polarizability [Formula: see text], population pOP, intra [Formula: see text], and inter [Formula: see text] repulsions, and density ρOP, of polyatomic systems were calculated, analyzed, and correlated. Several trends are shown for these properties, which are rationalized by the balance of some well-known effects, such as, electron donor/withdrawing character and electronegativity. The overlap properties of unusual bonds are also analyzed, revealing an OZn4(OOCH)6 structure with four equivalent Zn-O chemical bonds with overlap properties like the O-O bond in H2O2, while in protonated methane [Formula: see text], it is observed that a CH3⋯[Formula: see text] bond pattern at the equilibrium structure changes to a [Formula: see text]⋯H2 pattern upon dissociation. Charge-shift resonance energies, atom-in-molecule properties, and the lone-pair-bond-weakening effects are related to the overlap properties, which can provide alternative views and insights into chemical bonds. Graphical abstract A chemical bond analysis approach based on its overlap properties is presented for the first time. The model was applied directly to 25 diatomics and for 28 bonds in polytomics employing localized molecular orbitals. Correlations of the overlap properties with the charge-shift resonance energies and with atom-in-molecule (AIM) properties were uncovered. In addition, it provided insights into the Zn-O bonds in the unusual OZn4(OOCH)6 system as well as in the bonding patterns of [Formula: see text] at equilibrium and upon dissociation.