# Global Analysis of Polyfluorene via AB-Type Suzuki–Miyaura Polymerization: Empirical and Mechanistic Rationalization of Structural and Reaction Parameters on Molar Mass, Dispersity, and Yield

## TL;DR

This paper analyzes how to optimize the synthesis of polyfluorene polymers using a specific polymerization method to achieve desired properties like molar mass and dispersity.

## Contribution

A global algorithmic analysis of AB-type Suzuki-Miyaura polymerization data to identify optimal conditions for high fidelity and yield.

## Key findings

- SCTP fidelity is maintained with monomer-to-catalyst ratios up to 500 using tBu3P-based Pd precatalysts and boronate monomers.
- Monomer-to-catalyst ratios up to 25 typically follow ideal SCTP behavior.
- The study provides a dataset and machine learning-ready results for further analysis.

## Abstract

The preparation of conjugated polymers with precisely
tunable optoelectronic
properties is based on modern polymerization techniques. In addition
to conventional step-growth polycondensation for the underlying C–C
coupling steps, the Suzuki-Miyaura catalyst-transfer polymerization
(SCTP) continues to attract great interest, as it enables chain growth
with controlled molar masses, dispersity values, and end group fidelity.
The combination of these beneficial properties allows for use in defined
block copolymers or as functional building blocks in functional polymer
architectures aiming to control energy and charge transfer at the
macromolecular level. For an ideal SCTP mechanism, a ring-walking
step is crucialand many experimental parameters contribute
to the overall success of the polymerization to tailor the desired
degree of polymerization, low dispersity values, and high yields.
Many reports explored specific combinations within the available parameter
space, yet a unifying analysis to identify limitations as well as
promising future directions to advance synthetic methodologies is
needed. In this work, all available experimental data for the AB-type
2,7-linked poly­(fluorene) is collected, and a detailed algorithmic
global analysis is presented, including the tabulated results for
machine learning and reinspection of the collected raw data. It is
found that SCTP is typically obeyed for monomer-to-catalyst ratios
up to 25, while the combination of
t
Bu3P-based Pd precatalysts and boronate-based monomers enables
excellent SCTP fidelity with monomer-to-catalyst ratios up to 500.