Recent Developments of Nontraditional Single-Molecule Toroics.

Single-molecule toroics (SMTs), defined as a type of molecules with toroidal arrangement of magnetic moment associated with bi-stable non-magnetic ground states, are promising candidates for high-density information storage and the development of molecule based multiferroic materials with linear magneto-electric coupling and multiferroic behavior. The design and synthesis of SMTs by arranging the magnetic anisotropy axis in a circular pattern at the molecular level have been of great interest to scientists for last two decades since the first detection of the SMT behavior in the seminal Dy3 molecules. DyIII ion has long been the ideal candidate for constructing SMTs due to its Kramer ion nature as well as high anisotropy. Nevertheless, other LnIII ions such as TbIII and HoIII ions, as well as some paramagnetic transition metal ions, have also been used to construct many nontraditional SMTs. Therefore, we review the progress in the studies of SMTs based on the nontraditional perspective, ranging from the 3D topological to 1D&2D&3D polymeric SMTs, and 3d-4f to non Dy-based SMTs. We hope the understanding we provide about nontraditional SMTs will be helpful in designing novel SMTs.

Elevating the Performance of Heterometallic 3d/4f SMMs: The Role of Diamagnetic CoIII and ZnII Ions in Magnetization Dynamics.

Recent advances in the synthesis of 3d/4f Single-Molecule Magnets (SMMs) have revealed the effective role of incorporating diamagnetic CoIII or ZnII ions to enhance the magnetic properties of LnIII ions. This concept highlights notable examples of CoIII/LnIII and ZnII/LnIII SMMs documented in the recent literature, illustrating how the selection of various peripheral and/or bridging ligands can modulate the magnetic anisotropy of 4f metal ions, thereby increasing their energy barriers.

Strength of motivation of 1st year dental students of a dental institution: A cross-sectional study.

Objective: The study aims to evaluate the motivation levels of dental students, with an emphasis on first-year BDS students, by utilizing the Strength of Motivation for Medical School (SMMS) questionnaire. Methods: It was a descriptive cross-sectional quantitative study targeting 89 first-year BDS students enrolled at Lahore Medical and Dental College from 5th June to 18th August 2023. The Strength of Motivation for Medical School (SMMS) questionnaire was given to the participants after ethical board approval. Data analysis was done through SPSS version 26. The SMMS score was presented as the means standard deviation and an independent t-test was used to find the difference between the groups. The maximum score possible is 80 and the minimum is 16. The higher the score, the greater the strength of motivation. Results: In this study, a total of 89 first-year BDS students completed motivation questionnaires, with 34.8% males and 65.2% females. The average age was 19.92 ± 3.13. The overall Strength of Motivation Score (SMMS) averaged 45.53 ± 6.82. Results indicated 9% low, 89.9% moderate, and 1.1% strong motivation. Females had a slightly higher mean SMMS (45.93 ± 6.88) than males (44.80 ± 6.76), but the difference was deemed insignificant (p = 0.462) via independent t-test. Conclusion: Motivation is vital to achieving excellence in academic pursuits. Nevertheless, there isn't a single criterion that can be utilized to assess success and motivation. Our primary focus must be on every possible outcome of success, not just the scoring criteria.

Influence of the Coordinated Transition Metal Ion on Magnetic Relaxation of Lanthanide Based Complexes with Imino Nitroxide Biradical Ligands.

In spite of achievement of a lot of Ln-radical SMMs, how to improve magnetic behavior of Ln-radical system remains challenging. Here, two series of Ln-radical complexes have successfully been built using an imino nitroxide biradical, namely, [Ln2 (hfac)6 (ImPhPyobis)2 ] (LnIII =Gd 1, Tb 2, Dy 3) and [Ln2 Cu2 (hfac)10 (ImPhPyobis)2 ] (LnIII =Gd 4, Dy 5; hfac=hexafluoroacetylacetonate and ImPhPyobis=5-(4-oxypyridinium-1-yl)-1,3-bis(1'-oxyl-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene). For these biradical-metal complexes, two imino nitroxide biradicals bind two Ln(III) ions via their oxygen atoms coming from 4-oxypyridinium units to produce a binuclear {Ln2 O2 } unit. Those imino nitroxide groups are free for complexes 1-3, however one of imino nitroxide groups of the biradical is ligated to the copper(II) ion for complexes 4 and 5. The distinct magnetic relaxation behaviors are observed for two Dy derivatives, as revealed by ac magnetic studies: complex 3 presents one magnetic process with the effective energy barrier(Ueff ) of 74.0 K while complex 5 exhibits dual relaxation processes with Ueff values for the fast- and slow-relaxation being 20.2 K and 30.9 K, respectively, which implies that the second coordination sphere of Dy ion plays a critical role for magnetic relaxation.

Applying Unconventional Spectroscopies to the Single-Molecule Magnets, Co(PPh3 )2 X2 (X=Cl, Br, I): Unveiling Magnetic Transitions and Spin-Phonon Coupling.

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh3 )2 X2 (Co-X; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X, showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.

Spectroscopic Studies of the Magnetic Excitation and Spin-Phonon Couplings in a Single-Molecule Magnet.

Large separations between ground and excited magnetic states in single-molecule magnets (SMMs) are desirable to reduce the likelihood of spin reversal in the molecules. Spin-phonon coupling is a process leading to magnetic relaxation. Both the reversal and coupling, making SMMs lose magnetic moments, are undesirable. However, direct determination of large magnetic states separations (>45 cm-1 ) is challenging, and few detailed investigations of the spin-phonon coupling have been conducted. The magnetic separation in [Co(12-crown-4)2 ](I3 )2 (12-crown-4) (1) is determined and its spin-phonon coupling is probed by inelastic neutron scattering (INS) and far-IR spectroscopy. INS, using oriented single crystals, shows a magnetic transition at 49.4(1.0) cm-1 . Far-IR reveals that the magnetic transition and nearby phonons are coupled, a rarely observed phenomenon, with spin-phonon coupling constants of 1.7-2.5 cm-1 . The current work spectroscopically determines the ground-excited magnetic states separation in an SMM and quantifies its spin-phonon coupling, shedding light on the process causing magnetic relaxation.

Heterometallic Zn3 Ln3 Ensembles Containing (µ6 -CO3 ) Ligand and Triangular Disposition of Ln3+ ions: Analysis of Single-Molecule Toroic (SMT) and Single-Molecule Magnet (SMM) Behavior.

Two new heterometallic Zn3 Ln3 (Ln3+ =Dy, Tb) complexes, with a double triangular topology of the metal ions, have been assembled from the polytopic Mannich base ligand 6,6'-{[2-(dimethylamino)ethylazanediyl]bis(methylene)}bis(2-methoxy-4-methylphenol) (H2 L) with the aid of an in situ generated carbonate ligand from atmospheric CO2 fixation. Theoretical calculations indicate axial ground states for the Ln3+ ions in these complexes, with their local magnetic moments being almost coplanar and tangential to the Ln3+ atoms that define the equilateral triangle. Therefore, they can be considered as single-molecule toroics (SMTs) with almost zero total magnetic moment. Micro-SQUID measurements on the Dy3+ counterpart show hysteresis loops below 3 K that have an S-shape, with large coercive fields opening upon cooling. This behavior is typical of a single molecule magnet (SMM) with very slow zero-field relaxation. At around ±0.35 T, the loops have a broad step, which is due to a direct relaxation process and corresponds to an acceleration of the relaxation of the magnetization, also observed at this magnetic field from ac susceptibility measurements. Simulations suggest that the broad step corresponds to two level avoidance of crossing points where the spin chiral Kramers doublet meets excited states of the coupled manifold, whose position is defined by exchange and dipole interactions. The Tb3+ counterpart does not exhibit SMM behavior, which is due to the fact that the degeneracy of the ground state of the exchange coupled system is lifted at zero field, thus favoring quantum tunneling of magnetization (QTM).

Role of Magnetic Exchange Interactions in the Magnetization Relaxation of {3d-4f} Single-Molecule Magnets: A Theoretical Perspective.

Combined density functional and ab initio calculations are performed on two isomorphous tetranuclear {Ni3 (III) Ln(III) } star-type complexes [Ln=Gd (1), Dy (2)] to shed light on the mechanism of magnetic exchange in 1 and the origin of the slow magnetization relaxation in complex 2. DFT calculations correctly reproduce the sign and magnitude of the J values compared to the experiments for complex 1. Acute ∢Ni-O-Gd bond angles present in 1 instigate a significant interaction between the 4fxyz orbital of the Gd(III) ion and 3d${{_{x{^{2}}- y{^{2}}}}}$ orbital of the Ni(II) ions, leading to rare and strong antiferromagnetic Ni⋅⋅⋅Gd interactions. Calculations reveal the presence of a strong next-nearest-neighbour Ni⋅⋅⋅Ni antiferromagnetic interaction in complex 1 leading to spin frustration behavior. CASSCF+RASSI-SO calculations performed on complex 2 suggest that the octahedral environment around the Dy(III) ion is neither strong enough to stabilize the mJ |±15/2〉 as the ground state nor able to achieve a large ground-state-first-excited-state gap. The ground-state Kramers doublet for the Dy(III) ion is found to be the mJ |±13/2〉 state with a significant transverse anisotropy, leading to very strong quantum tunneling of magnetization (QTM). Using the POLY_ANISO program, we have extracted the JNiDy interaction as -1.45 cm(-1) . The strong Ni⋅⋅⋅Dy and next-nearest-neighbour Ni⋅⋅⋅Ni interactions are found to quench the QTM to a certain extent, resulting in zero-field SMM behavior for complex 2. The absence of any ac signals at zero field for the structurally similar [Dy(AlMe4 )3 ] highlights the importance of both the Ni⋅⋅⋅Dy and the Ni⋅⋅⋅Ni interactions in the magnetization relaxation of complex 2. To the best of our knowledge, this is the first time that the roles of both the Ni⋅⋅⋅Dy and Ni⋅⋅⋅Ni interactions in magnetization relaxation of a {3d-4f} molecular magnet have been established.

Facile interchange of 3d and 4f ions in single-molecule magnets: stepwise assembly of [Mn4 ], [Mn3Ln] and [Mn2Ln2 ] cages within calix[4]arene scaffolds.

The central Mn(II) ions in a series of calix[4]arene-stabilised butterflies can be sequentially replaced with Ln(III) ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of Mn(II) for Gd(III) allows for the examination of the transferability of spin-Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low-lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single-ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TM(II/III) (TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p-tBu-calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different "guests" within structurally robust "hosts".

Magnetodielectric Effect in a Triangular Dysprosium Single-Molecule Toroics.

Single-molecule toroics are molecular magnets with vortex distribution of magnetic moments. The coupling between magnetic and electric properties such as the magnetodielectric effect will provide potential applications for them. Herein, the observation of significant magnetodielectric effect in a triangular Dy3 crystal with toroidal magnetic moment and multiple magnetic relaxations is reported. The analysis of magnetic and electric properties implies that the magnetodielectric effect is closely related to the strong spin-lattice coupling, magnetic interactions of Dy3+ ions, as well as molecular packing models.

Double Immunohistochemical Labelling of PRAME and Melan A in Slow Mohs Biopsy Margin Assessment of Lentigo Maligna and Lentigo Maligna Melanoma.

Introduction: Lentigo maligna (LM) and lentigo maligna melanoma (LMM) predominantly affect the head and neck areas in elderly patients, presenting as challenging ill-defined pigmented lesions with indistinct borders. Surgical margin determination for complete removal remains intricate due to these characteristics. Morphological examination of surgical margins is the key form of determining successful treatment in LM/LMM and underpin the greater margin control provided through the Slow Mohs micrographic surgery (SMMS) approach. Recent assessments have explored the use of immunohistochemistry (IHC) markers, such as Preferentially Expressed Antigen in Melanoma (PRAME), to aid in LM/LMM and margin evaluation, leveraging the selectivity of PRAME labelling in malignant melanocytic neoplasms. Methods: A Novel double-labelling (DL) method incorporating both PRAME and MelanA IHC was employed to further maximise the clinical applicability of PRAME in the assessment of LM/LMM in SMMS biopsies. The evaluation involved 51 samples, comparing the results of the novel DL with respective single-labelling (SL) IHC slides. Results: The findings demonstrated a significant agreement of 96.1% between the DL method and SL slides across the tested samples. The benchmark PRAME SL exhibited a sensitivity of 91.3% in the SMMS specimens and 67.9% in histologically confirmed positive margins. Discussion: This study highlights the utility of PRAME IHC and by extension PRAME DL as an adjunctive tool in the assessment of melanocytic tumours within staged excision margins in SMMS samples.

Thermo-Mechanical Characterization of 4D-Printed Biodegradable Shape-Memory Scaffolds Using Four-Axis 3D-Printing System.

This study was conducted on different models of biodegradable SMP (shape-memory polymer) scaffolds. A comparison was conducted utilizing a basic FDM (fused deposition modeling)/MEX (material extrusion) printer with a standard printing technique and a novel, modified, four-axis printing method with a PLA (poly lactic acid) polymer as the printing material. This way of making the 4D-printed BVS (biodegradable vascular stent) made it possible to achieve high-quality surfaces due to the difference in printing directions and improved mechanical properties-tensile testing showed a doubling in the elongation at break when using the four-axis-printed specimen compared to the regular printing, of 8.15 mm and 3.92 mm, respectfully. Furthermore, the supports created using this method exhibited a significant level of shape recovery following thermomechanical programming. In order to test the shape-memory effect, after the thermomechanical programming, two approaches were applied: one approach was to heat up the specimen after unloading it inside temperature chamber, and the other was to heat it in a warm bath. Both approaches led to an average recovery of the original height of 99.7%, while the in-chamber recovery time was longer (120 s) than the warm-bath recovery (~3 s) due to the more direct specimen heating in the latter case. This shows that 4D printing using the newly proposed four-axis printing is an effective, promising technique that can be used in the future to make biodegradable structures from SMP.

Influence of microstructural alterations of liquid metal and its interfacial interactions with rubber on multifunctional properties of soft composite materials.

Liquid metal (LM)-based polymer composites are currently new breakthrough and emerging classes of soft multifunctional materials (SMMs) having immense transformative potential for soft technological applications. Currently, room-temperature LMs, mostly eutectic gallium­indium and Galinstan alloys are used to integrate with soft polymer due to their outstanding properties such as high conductivity, fluidity, low adhesion, high surface tension, low cytotoxicity, etc. The microstructural alterations and interfacial interactions controlling the efficient integration of LMs with rubber are the most critical aspects for successful implementation of multifunctionality in the resulting material. In this review article, a fundamental understanding of microstructural alterations of LMs to the formation of well-defined percolating networks inside an insulating rubber matrix has been established by exploiting several existing theoretical and experimental studies. Furthermore, effects of the chemical modifications of an LM surface and its interfacial interactions on the compatibility between solid rubber and fluid filler phase have been discussed. The presence of thin oxide layer on the LM surface and the effects and challenges it poses to the adequate functionalization of these materials have been discussed. Plausible applications of SMMs in different soft matter technologies, like soft robotics, flexible electronics, soft actuators, sensors, etc. have been provided. Finally, the current technical challenges and further prospective to the development of SMMs using non­silicone rubbers have been critically discussed. This review is anticipated to infuse a new impetus to the associated research communities for the development of next generation SMMs.

Advances in the development of biodegradable coronary stents: A translational perspective.

Implantation of cardiovascular stents is an important therapeutic method to treat coronary artery diseases. Bare-metal and drug-eluting stents show promising clinical outcomes, however, their permanent presence may create complications. In recent years, numerous preclinical and clinical trials have evaluated the properties of bioresorbable stents, including polymer and magnesium-based stents. Three-dimensional (3D) printed-shape-memory polymeric materials enable the self-deployment of stents and provide a novel approach for individualized treatment. Novel bioresorbable metallic stents such as iron- and zinc-based stents have also been investigated and refined. However, the development of novel bioresorbable stents accompanied by clinical translation remains time-consuming and challenging. This review comprehensively summarizes the development of bioresorbable stents based on their preclinical/clinical trials and highlights translational research as well as novel technologies for stents (e.g., bioresorbable electronic stents integrated with biosensors). These findings are expected to inspire the design of novel stents and optimization approaches to improve the efficacy of treatments for cardiovascular diseases.

Single Molecule Magnets of Co2 and Co2La MOFs Synthesized by New Schiff Base Ligand N,N'-bis(o-Vanillinidene) Ethylenediamine (o-VEDH2).

Schiff base ligand N,N'-bis(o-vanillinidene) ethylenediamine (o-VEDH2) has been employed to synthesize new [CoIICoIV(o-VED)(OAc)2(µ2-OAc)(OMe)]•MeOH (1) and [ Co 2 IV (o-VED)2(en)2(NCCH3)(OCH3)][La(NO3)6]( NO 3 - )•2MeOH•MeCN•H2O (2) metal-organic frameworks (MOFs) that have interesting single molecule magnets (SMMs) property. The synthesized complexes are characterized by single crystal X-ray diffraction, fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy, and squid magnetic measurement. Single crystal X-ray data show that both complexes crystallize in the monoclinic crystal system with P21/c(14) and P21/n(14) space groups and generate unique MOF-like structures. Overall, both the metal centers of 1 form octahedral geometry with a butterfly core structure. Variable temperature (T) and field (H) solid-state direct-current (dc) and alternative current (ac) magnetic susceptibility measurements were performed on both the complexes over 1.8 to 300 K, which exhibited a ground state spins (S) of 4 and 5 of complexes 1 and 2, respectively. The AC out-phase and in-phase properties of complexes show SMMs. Other properties such as optical, sensing, and DNA-binding interactions were also investigated by the complexes. Complexes 1 and 2 have energy band gaps of 3.7 and 3.03 eV indicating semiconductor properties. Simultaneously, complex 1 was found to sense H2O2 with a rate constant (k) = 1.59 × 10-4 s-1, whereas complex 2 was found to bind with calf-thymus-DNA by intercalation mode with binding constant (K b ) of 1.22 × 105 M-1.

Octanuclear Ni4 Ln4 Coordination Aggregates from Schiff Base Anion Supports and Connecting of Two Ni2 Ln2 Cubes: Syntheses, Structures, and Magnetic Properties.

A family of 3d-4f aggregates have been reported through guiding the dual coordination modes of ligand anion (HL- ) and in situ generated ancillary bridge driven self-assembly coordination responses toward two different types of metal ions. Reactions of lanthanide(III) nitrate (Ln=Gd, Tb, Dy, Ho and Yb), nickel(II) acetate and phenol-based ditopic ligand anion of 2-[{(2-hydroxypropyl)imino}methyl]-6-methoxyphenol (H2 L) in MeCN-MeOH (3 : 1) mixture and LiOH provided five new octanuclear Ni-4f coordination aggregates from two Ni2 Ln2 cubanes. Single-crystal X-ray diffraction analysis reveals that all the members of the family are isostructural, with the central core formed from the coupling of two distorted [Ni2 Ln2 O4 ] heterometallic cubanes [Ni2 Ln2 (HL)2 (µ3 -OH)2 (OH)(OAc)4 ]+ (Ln=Gd (1), Tb (2), Dy (3), Ho (4) and Yb (5)). Higher coordination demand of 4f ions induced the coupling of the two cubes by (OH)(OAc)2 bridges. Variable temperature magnetic study reveals weak coupling between the Ni2+ and Ln3+ ions. For the Tb (2) and Dy (3) analogs, the compounds are SMMs without an applied dc field, whereas the Gd (1) analogue is not an SMM. The observation revealed thus that the anisotropy of the Ln3+ ions is central to display the SMM behavior within this structurally intriguing family of compounds.

Role of Ab Initio Calculations in the Design and Development of Organometallic Lanthanide-Based Single-Molecule Magnets.

Single-molecule magnets based on lanthanides are very attractive due to their potential applications proposed in the area of microelectronic devices. Very recent advances in this area are due to the blend of conventional lanthanide chemistry with organometallic ligands, and several breakthrough achievements are attained with this combination. Ab initio methods based on multi-reference CASSCF calculations are playing a vital role in the design and development of such molecules. In this minireview, we aim to appraise various contributions in the area of organometallic lanthanide complexes (those containing lanthanide-carbon bonds) and describe how these robust wavefunction-based methods have played a constructive role not only in rationalizing the observed magnetic properties but also proven to be a potential predictive tool with some selected examples.

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier.

Chiral bipyrimidine-bridged dinuclear LnIII complexes of general formula [(µ-bipym){((+)-tfacam)3Ln}2] and [(µ-bipym){((-)-tfacam)3Ln}2], have been prepared from the assembly of Ln(AcO)3·nH2O (LnIII = Dy, Gd), (+)/(-)-3-(trifluoroacetyl)camphor enantiopure ligands ((+)/(-)-Htfacam) and bipyrimidine (bipym). The structure and chirality of these complexes have been supported by single-crystal X-Ray diffraction and circular dichroism. The study of the magnetic properties of the GdIII complexes revealed a very weak antiferromagnetic interaction between the GdIII ions through the bipyrimidine bridging ligand. Ab initio CASSCF calculations indicated that the ground Kramers doublet (KD) of both DyIII centers is almost purely axial with the anisotropy axis located close to the two tfacam-ligands at opposite sides of each DyIIIatom, which create an axial crystal field. In keeping with this, ac dynamic measurements indicated slow relaxation of the magnetization at zero field with U eff = 55.1 K, a pre-exponential factor of τo = 2.17·10-6 s and τQTM = 8 µs. When an optimal dc field of 0.1 T is applied, QTM is quenched and U eff increases to 75.9 K with τo = 6.16 × 10-7 s. The DyN2O8 coordination spheres and SMM properties of [(µ-bipym){((+)-tfacam)3Ln}2] and their achiral [(Dy(ß-diketonate)3)2(µ-bpym)]analogous have been compared and a magneto-structural correlation has been established, which has been supported by theoretical calculations. In contrast to the GdIII compounds, the magnetic exchange interaction between the DyIII ions has been calculated to be very weak and, generally, ferromagnetic in nature. Relaxation mechanisms for [(µ-bipym){((+)-tfacam)3Ln}2] and previously reported analogous have been proposed from ab initio calculations. As the magnetic exchange interaction found to be very weak, the observed magnetization blockade in these systems are primarily dictated by the single ion anisotropy of DyIII ions.

Role of π-Radicals in the Spin Connectivity of Clusters and Networks of Tb Double-Decker Single Molecule Magnets.

When single molecule magnets (SMMs) self-assemble into 2D networks on a surface, they interact via the π-electrons of their ligands. This interaction is relevant to the quantum entanglement between molecular qubits, a key issue in quantum computing. Here, we examine the role played by the unpaired radical electron in the top ligand of Tb double-decker SMMs by comparing the spectroscopic features of isolated and 2D assembled entities on surfaces. High-resolution scanning tunneling microscopy (STM) is used to evidence experimentally the Kondo resonance of the unpaired radical spins in clusters and islands and its quenching due to up-pairing at orbital overlaps. The presence or the absence of the Kondo feature in the dI/dV maps turns out to be a good measure of the lateral interaction between molecules in 2D networks. In a 2D cluster of molecules, the π-orbital lobes that are linked through the orbital overlap show paired-up electron wave function (one singly occupied molecular orbital (SOMO) with spin-up and the other with spin-down) and therefore do not experience the Kondo resonance in the experiment. As a result, small clusters built by STM-assisted manipulation of molecules show alternating Kondo features of quantum mechanical origin, from the monomer to the dimer and the trimer. On the other hand, when the TbPc2 molecular clusters grow larger and form extended domains, a geometric rearrangement occurs, leading to the quenching of the Kondo signal on one lobe out of two. The even distribution of overlapping (SOMO) lobes on the perimeter of the molecule is induced by the square symmetry of the semi-infinite lattice and clearly distinguishes the lattice from the clusters.